Reduced Polymer Formation For Selective Ethylene Oligomerizations

ABSTRACT

Disclosed herein are processes, systems, and reaction systems for the oligomerization of ethylene to form an ethylene oligomer product in a reaction zone using a catalyst system having i) a chromium component comprising a heteroatomic ligand chromium compound complex of the type disclosed herein, and ii) an aluminoxane. A C 3+  olefin can be present in the reaction zone for a period of time, where the C 3+  olefin is not an ethylene oligomer formed in-situ within the reaction zone.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of and claims priority to U.S. patentapplication Ser. No.15/167,024 filed May 27, 2016, published as U.S.Patent Application Publication US 2017/0341999 A1, and entitled “ReducedPolymer Formation for Selective Ethylene Oligomerizations,” which isincorporated by reference herein in its entirety.

TECHNICAL FIELD

The present disclosure relates to processes, system, and reaction systemconfigurations for oligomerization of ethylene.

BACKGROUND

The development of alpha olefin oligomerization techniques for theselective production of linear alpha olefins (C₆ to C₂₀) which do notutilize triethylaluminum (TEA) as part of the catalyst system has been achallenge. Both the economics and relative efficiency of TEA-basedtechniques have been difficult to match in alternative techniques. Somecommercial success has been achieved using alternative techniques whichuse homogeneous catalyst systems; however, these techniques requireextended secondary processing to recover the linear alpha olefins fromundesired fractions/products such as butene or waxes. Other alternativetechniques utilizing diphosphinyl amine chromium compound complexes havebeen developed as well. The diphosphinyl amine chromium compoundcomplexes based catalyst systems can produce desired linear alphaolefins without the drawbacks of the alternative techniques which usehomogeneous catalyst systems. There is an ongoing need for improvementsto diphosphinyl amine chromium compound complex (and related chromiumcompound complex) based oligomerization techniques.

SUMMARY

Disclosed is a process comprising: a) introducing into a reaction zonecontaining a C₃₊ olefin (any disclosed herein) and optionally an organicreaction medium (any disclosed herein) wherein the reaction zone issubstantially devoid of ethylene, i) ethylene ii) a catalyst systemcomprising (a) a chromium component comprising a chromium compound (anydescribed herein), (b) a heteroatomic ligand (any described herein), and(c) an aluminoxane (any disclosed herein); or alternatively, a catalystsystem comprising (a) a chromium component comprising a heteroatomicligand chromium compound complex (any described herein), and (b) analuminoxane (any disclosed herein), iii) the organic reaction medium,and iv) optionally hydrogen; and b) forming an ethylene oligomer productin the reaction zone; wherein the C₃₊ olefin is not an ethylene oligomerformed in-situ within the reaction zone.

Also disclosed is a process comprising: a) contacting in a reaction zonei) a C₃₊ olefin (e.g., any disclosed herein), ii) ethylene, iii) acatalyst system comprising (a) a chromium component comprising achromium compound (any described herein), (b) a heteroatomic ligand (anydescribed herein), and (c) an aluminoxane (any disclosed herein); oralternatively, a catalyst system comprising (a) a chromium componentcomprising a heteroatomic ligand chromium compound complex (anydescribed herein), and (b) an aluminoxane (any disclosed herein), iv) anorganic reaction medium (any disclosed herein), and v) optionallyhydrogen into the reaction zone; and c) forming an ethylene oligomerproduct; wherein the C₃₊ olefin is not an ethylene oligomer formedin-situ within the reaction zone.

Also disclosed is a process comprising: a) contacting i) ethylene, ii) acatalyst system comprising (a) a chromium component comprising achromium compound (any described herein), (b) a heteroatomic ligand (anydescribed herein), and (c) an aluminoxane (any disclosed herein); oralternatively, a catalyst system comprising (a) a chromium componentcomprising a heteroatomic ligand chromium compound complex (anydescribed herein), and (b) an aluminoxane (any disclosed herein), iii)an organic reaction medium (any described herein), and iv) optionallyhydrogen in a reaction zone; b) forming an ethylene oligomer product inthe reaction zone; wherein ethylene, the catalyst system, and theorganic reaction medium are introduced into the reaction zone and for aperiod of time a C₃₊ olefin is introduced into the reaction zone.

Also disclosed is a process comprising: a) feeding a catalyst system toa reaction zone, the catalyst system comprising i) a chromium componentcomprising a chromium compound (any described herein), ii) aheteroatomic ligand (any described herein), and iii) an aluminoxane (anydisclosed herein); or alternatively, a catalyst system comprising i) achromium component comprising a heteroatomic ligand chromium compoundcomplex (any described herein), and ii) an aluminoxane (any disclosedherein); b) for a period of time separately feeding to the reaction zonea feedstock mixture comprising ethylene and i) a C₃₊ olefin (e.g., anydescribed herein), and ii) at least a portion of an organic reactionmedium (e.g., any described herein), or iii) combinations of i) and ii);wherein the feedstock mixture is substantially free of the catalystsystem; c) contacting the catalyst system and the feedstock mixture inthe reaction zone; and d) forming an ethylene oligomer product in thereaction zone.

Also disclosed is a process comprising: a) contacting i) ethylene, ii)at least a portion of an organic reaction medium (e.g., any disclosedherein), and iii) for a period of time a C₃₊ olefin (e.g., any disclosedherein) to form a feedstock mixture; b) subsequent to a), contacting ina reaction zone the feedstock mixture with a catalyst system comprisingi) a chromium component comprising a chromium compound (any describedherein), ii) a heteroatomic ligand (any described herein), and iii) analuminoxane (any disclosed herein); or alternatively, a catalyst systemcomprising i) a chromium component comprising a heteroatomic ligandchromium compound complex (any described herein), and ii) an aluminoxane(any disclosed herein); and c) forming an ethylene oligomer product inthe reaction zone.

Also disclosed is a process comprising: a) diluting ethylene by additionof at least i) a portion of an organic reaction medium (any describedherein), ii) for a period of time a C₃₊ olefin (e.g., any describedherein), or iii) for a period of time at least a portion of an organicreaction medium (any described herein) and a C₃₊ olefin to form afeedstock mixture prior to contacting the ethylene with a catalystsystem in a reaction zone; b) contacting in the reaction zone thefeedstock mixture and the catalyst system, wherein the catalyst systemcomprises i) a chromium component comprising a chromium compound (anydescribed herein), ii) a heteroatomic ligand (any described herein), andiii) an aluminoxane (any disclosed herein); or alternatively, a catalystsystem comprising i) a chromium component comprising a heteroatomicligand chromium compound complex (any described herein), and ii) analuminoxane (any disclosed herein); and c) forming an ethylene oligomerproduct in the reaction zone.

Also disclosed is a system comprising: a) a feedstock mixture comprisingethylene, an organic reaction medium (e.g., any described herein), andfor a period of time a C₃₊ olefin (e.g., any described herein); b) acatalyst system comprising i) a chromium component comprising a chromiumcompound (any described herein), ii) a heteroatomic ligand (anydescribed herein), and iii) an aluminoxane (any disclosed herein); oralternatively, a catalyst system comprising i) a chromium componentcomprising a heteroatomic ligand chromium compound complex (anydescribed herein), and ii) an aluminoxane (any disclosed herein); and c)a reaction zone receiving the feedstock mixture separately from thecatalyst stream.

Also disclosed is a process comprising: a) feeding a catalyst system toa reaction zone, the catalyst system comprising i) a chromium componentcomprising a chromium compound (any described herein), ii) aheteroatomic ligand (any described herein), and iii) an aluminoxane (anydisclosed herein); or alternatively, a catalyst system comprising i) achromium component comprising a heteroatomic ligand chromium compoundcomplex (any described herein), and ii) an aluminoxane (any disclosedherein); b) separately feeding to the reaction zone a feedstock mixturecomprising i) ethylene, ii) an organic reaction medium (e.g., anydescribed herein), and iii) for a period of time a C₃₊ olefin (e.g., anydescribed herein) to contact the catalyst system; wherein during areaction zone startup the feedstock mixture C₃₊ olefin:ethylene weightratio periodically or continuously decreases; c) forming an ethyleneoligomer product in the reaction zone; and d) operating the reactionzone in about steady-state conditions subsequent to the reaction zonestart-up; wherein the period of time is a reaction zone period of timeor a C₃₊ olefin/ethylene feed period of time.

Also disclosed is a process for startup of a reaction zone, the processcomprising: for a period of time contacting in the reaction zone 1)ethylene, 2) a catalyst system comprising a) a chromium componentcomprising a chromium compound (any described herein), b) a heteroatomicligand (any described herein), and c) an aluminoxane (any disclosedherein); or alternatively, a catalyst system comprising a) a chromiumcomponent comprising a heteroatomic ligand chromium compound complex(any described herein), and b) an aluminoxane (any disclosed herein), 3)an organic reaction medium, and 4) optionally hydrogen to form anethylene oligomer product; wherein: the catalyst system is fed to thereaction zone, a feedstock mixture comprising i) ethylene, ii) anorganic reaction medium (any described herein), and iii) a C₃₊ olefin(any described herein) is fed to the reaction zone for a period of time,wherein the feedstock mixture is substantially free of the catalystsystem prior to the feedstock mixture contacting the catalyst system inthe reaction zone.

Also disclosed is a reaction system comprising: a reaction zone; a firstreaction zone inlet configured to introduce a catalyst system comprising(a) a chromium component comprising a chromium compound (any describedherein), (b) a heteroatomic ligand (any described herein), and (c) analuminoxane (any disclosed herein); or alternatively, a catalyst systemcomprising (a) a chromium component comprising a heteroatomic ligandchromium compound complex (any described herein), and (b) an aluminoxane(any disclosed herein) to the reaction zone; a second reaction zoneinlet configured to introduce ethylene, an organic reaction medium, andoptionally hydrogen to the reaction zone; a C₃₊ olefin feed line influid communication with the first reaction zone inlet, the secondreaction zone inlet, or a third reaction zone inlet configured tointroduce a C₃₊ olefin to the reaction zone; and one or more reactionzone outlets configured to discharge the reaction zone effluentcomprising an ethylene oligomer product from the reaction zone.

Also disclosed is a reaction system comprising: a reaction zone; areaction zone inlet configured to introduce a catalyst system, ethylene,an organic reaction medium, and a C₃₊ olefin to the reaction zone; anethylene feed line comprising ethylene, a C₃₊ olefin feed linecomprising a C₃₊ olefin, an organic reaction medium feed line comprisingan organic reaction medium and optionally a hydrogen feed linecomprising hydrogen all in fluid communication with the reaction zoneinlet, wherein the organic reaction medium feed line combines with theethylene feed line to form a feedstock mixture feed line in fluidcommunication with the reaction zone inlet; a catalyst system feed linecomprising catalyst system in fluid communication with the reaction zoneinlet, wherein the catalyst system feed line combines with the ethylenefeed line, the organic reaction medium feed line, the feedstock mixturefeed line, or a dispersed feedstock mixture feed line formed by passingthe feedstock mixture feed line through a mixing device; one or morereaction zone outlets configured to discharge the reaction zone effluentcomprising an ethylene oligomer product from the reaction zone, whereinthe catalyst system comprises (a) a chromium component comprising achromium compound (any described herein), (b) a heteroatomic ligand (anydescribed herein), and (c) an aluminoxane (any disclosed herein); oralternatively, a catalyst system comprising (a) a chromium componentcomprising a heteroatomic ligand chromium compound complex (anydescribed herein), and (b) an aluminoxane (any disclosed herein), andwherein the C₃₊ olefin feed line joins with one or more of the ethylenefeed line, the organic reaction medium feed line, the feedstock mixturefeed line, the dispersed feedstock mixture feed line, or a combined feedline formed by joining the catalyst system feed line and the dispersedfeedstock mixture feed line.

Also disclosed is a reaction system comprising: a reaction zone; a firstreaction zone inlet configured to introduce a catalyst system comprising(a) a chromium component comprising a chromium compound (any describedherein), (b) a heteroatomic ligand (any described herein), and (c) analuminoxane (any disclosed herein); or alternatively, a catalyst systemcomprising (a) a chromium component comprising a heteroatomic ligandchromium compound complex (any described herein), and (b) an aluminoxane(any disclosed herein) to the reaction zone; a second reaction zoneinlet configured to introduce ethylene and optionally hydrogen to thereaction zone; a third reaction zone inlet configured to introduce anorganic reaction medium to the reaction zone; a C₃₊ olefin feed line influid communication with one or more of the first reaction zone inlet,the second reaction zone inlet, the third reaction zone inlet, or afourth reaction zone inlet which is configured to introduce the C₃₊olefin directly to the reaction zone; and one or more reaction zoneoutlets configured to discharge the reaction zone effluent comprising anethylene oligomer product from the reaction zone.

BRIEF DESCRIPTION OF THE DRAWINGS

For a detailed description, reference will now be made to theaccompanying drawings

FIG. 1 shows a process flow diagram of a reaction system according tothe present disclosure.

FIG. 2 shows a process flow diagram of another reaction system accordingto the present disclosure.

FIG. 3 shows a process flow diagram of another reaction system accordingto the present disclosure.

DETAILED DESCRIPTION

In the description herein, various ranges and/or numerical limitationscan be expressly stated below. It should be recognized that unlessstated otherwise, it is intended that endpoints are to beinterchangeable. Further, any ranges include iterative ranges of likemagnitude falling within the expressly stated ranges or limitations.

Furthermore, various modifications can be made within the scope of theinvention as herein intended, and embodiments of the invention caninclude combinations of features other than those expressly claimed. Inparticular, flow arrangements other than those expressly describedherein are within the scope of the invention.

Unless otherwise specified, the terms “contact” and “combine,” and theirderivatives, can refer to any addition sequence, order, or concentrationfor contacting or combining two or more components of the disclosedembodiments. Combining or contacting of oligomerization components canoccur in one or more reaction zones under suitable contact conditionssuch as temperature, pressure, contact time, flow rates, etc.

Regarding claim transitional terms or phrases, the transitional term“comprising”, which is synonymous with “including,” “containing,”“having” or “characterized by,” is inclusive or open-ended and does notexclude additional, unrecited elements or method steps. The transitionalphrase “consisting of” excludes any element, step, or ingredient notspecified in the claim. The transitional phrase “consisting essentiallyof” limits the scope of a claim to the specified materials or steps andthose that do not materially affect the basic and novelcharacteristic(s) of the claimed invention. A “consisting essentiallyof” claim occupies a middle ground between closed claims that arewritten in a “consisting of” format and fully open claims that aredrafted in a “comprising” format. Absent an indication to the contrary,when describing a compound or composition “consisting essentially of” isnot to be construed as “comprising,” but is intended to describe therecited component that includes materials which do not significantlyalter composition or method to which the term is applied. For example, afeedstock consisting of a material A can include impurities typicallypresent in a commercially produced or commercially available sample ofmaterial A. When a claim includes different features and/or featureclasses (for example, a method step, feedstock features, and/or productfeatures, among other possibilities), the transitional terms comprising,consisting essentially of, and consisting of apply only to the featureclass that is utilized and it is possible to have different transitionalterms or phrases utilized with different features within a claim. Forexample a method can comprise several recited steps (and othernon-recited steps) but utilize a catalyst system preparation consistingof specific steps can utilize a catalyst system comprising recitedcomponents and other non-recited components.

Within this specification, use of “comprising” or an equivalentexpression contemplates the use of the phrase “consisting essentiallyof,” “consists essentially of,” or equivalent expressions as alternativeembodiments to the open-ended expression. Additionally, use of“comprising” or an equivalent expression or use of “consistingessentially of” in the specification contemplates the use of the phrase“consisting of,” “consists of,” or equivalent expressions as analternative to the open-ended expression or middle ground expression,respectively. For example, “comprising” should be understood to include“consisting essentially of,” and “consisting of” as alternativeembodiments for the aspect, features, and/or elements presented in thespecification unless specifically indicated otherwise.

While compositions and methods are described in terms of “comprising”various components or steps, the compositions and methods can also“consist essentially of” or “consist of” the various components orsteps.

The terms “a,” “an,” and “the” are intended, unless specificallyindicated otherwise, to include plural alternatives, e.g., at least one.For instance, the disclosure of “a trialkylaluminum compound” is meantto encompass one trialkylaluminum compound, or mixtures or combinationsof more than one trialkylaluminum compound unless otherwise specified.

Unless otherwise indicated, the definitions are applicable to thisdisclosure. If a term is used in this disclosure but is not specificallydefined herein, the definition from the IUPAC Compendium of ChemicalTerminology, 2^(nd) Ed (1997), can be applied, as long as thatdefinition does not conflict with any other disclosure or definitionapplied herein, or render indefinite or non-enabled any claim to whichthat definition can be applied. To the extent that any definition orusage provided by any document incorporated herein by referenceconflicts with the definition or usage provided herein, the definitionor usage provided herein controls.

Groups of elements of the Periodic Table are indicated using thenumbering scheme indicated in the version of the Periodic Table ofelements published in Chemical and Engineering News, 63(5), 27, 1985. Insome instances, a group of elements can be indicated using a common nameassigned to the group; for example, alkali metals for Group 1 elements,alkaline earth metals (or alkaline metals) for Group 2 elements,transition metals for Groups 3-12 elements, and halogens for Group 17elements.

For any particular compound disclosed herein, the general structure orname presented is also intended to encompass all structural isomers,conformational isomers, and stereoisomers that can arise from aparticular set of substituents, unless indicated otherwise. Thus, ageneral reference to a compound includes all structural isomers unlessexplicitly indicated otherwise; e.g., a general reference to hexeneincludes 1-hexene, 2-hexene, 3-hexene, and any other hydrocarbon having6 carbon atoms (linear, branched or cyclic) and a single carbon carbondouble bond. Additionally, the reference to a general structure or nameencompasses all enantiomers, diastereomers, and other optical isomerswhether in enantiomeric or racemic forms, as well as mixtures ofstereoisomers, as the context permits or requires. For any particularformula or name that is presented, any general formula or name presentedalso encompasses all conformational isomers, regioisomers, andstereoisomers that can arise from a particular set of substituents.

A chemical “group” is described according to how that group is formallyderived from a reference or “parent” compound, for example, by thenumber of hydrogen atoms formally removed from the parent compound togenerate the group, even if that group is not literally synthesized inthis manner. By way of example, an “alkyl group” formally can be derivedby removing one hydrogen atom from an alkane, while an “alkylene group”formally can be derived by removing two hydrogen atoms from an alkane.Moreover, a more general term can be used to encompass a variety ofgroups that formally are derived by removing any number (“one or more”)hydrogen atoms from a parent compound, which in this example can bedescribed as an “alkane group,” and which encompasses an “alkyl group,”an “alkylene group,” and materials have three or more hydrogens atoms,as necessary for the situation, removed from the alkane. Throughout, thedisclosure of a substituent, ligand, or other chemical moiety canconstitute a particular “group” implies that the well-known rules ofchemical structure and bonding are followed when that group is employedas described. When describing a group as being “derived by,” “derivedfrom,” “formed by,” or “formed from,” such terms are used in a formalsense and are not intended to reflect any specific synthetic methods orprocedure, unless specified otherwise or the context requires otherwise.

The term “organyl group” is used herein in accordance with thedefinition specified by IUPAC: an organic substituent group, regardlessof functional type, having one free valence at a carbon atom. Similarly,an “organylene group” refers to an organic group, regardless offunctional type, derived by removing two hydrogen atoms from an organiccompound, either two hydrogen atoms from one carbon atom or one hydrogenatom from each of two different carbon atoms. An “organic group” refersto a generalized group formed by removing one or more hydrogen atomsfrom carbon atoms of an organic compound. Thus, an “organyl group,” an“organylene group,” and an “organic group” can contain organicfunctional group(s) and/or atom(s) other than carbon and hydrogen, thatis, an organic group can comprise functional groups and/or atoms inaddition to carbon and hydrogen. For instance, non-limiting examples ofatoms other than carbon and hydrogen include halogens, oxygen, nitrogen,phosphorus, and the like. Non-limiting examples of functional groupsinclude ethers, aldehydes, ketones, esters, sulfides, amines,phosphines, and so forth. An “organyl group,” “organylene group,” or“organic group” can be aliphatic, inclusive of being cyclic or acyclic,or can be aromatic. “Organyl groups,” “organylene groups,” and “organicgroups” also encompass heteroatom-containing rings,heteroatom-containing ring systems, heteroaromatic rings, andheteroaromatic ring systems. “Organyl groups,” “organylene groups,” and“organic groups” can be linear or branched unless otherwise specified.Finally, it is noted that the “organyl group,” “organylene group,” or“organic group” definitions include “hydrocarbyl group,” “hydrocarbylenegroup,” “hydrocarbon group,” respectively, and “alkyl group,” “alkylenegroup,” and “alkane group,” respectively, as members.

For the purposes of this application, the term or variations of the term“organyl group consisting of inert functional groups” refers to anorganyl group wherein the organic functional group(s) and/or atom(s)other than carbon and hydrogen present in the functional group arerestricted to those functional group(s) and/or atom(s) other than carbonand hydrogen which do not complex with a metal compound and/or are inertunder the process conditions defined herein. Thus, the term or variationof the term “organyl group consisting of inert functional groups”further defines the particular organyl groups that can be present withinthe organyl group consisting of inert functional groups. Additionally,the term “organyl group consisting of inert functional groups” can referto the presence of one or more inert functional groups within theorganyl group. The term or variation of the term “organyl groupconsisting of inert functional groups” definition includes thehydrocarbyl group as a member (among other groups). Similarly, an“organylene group consisting of inert functional groups” refers to anorganic group formed by removing two hydrogen atoms from one or twocarbon atoms of an organic compound consisting of inert functionalgroups and an “organic group consisting of inert functional groups”refers to a generalized organic group consisting of inert functionalgroups formed by removing one or more hydrogen atoms from one or morecarbon atoms of an organic compound consisting of inert functionalgroups.

For purposes of this application, an “inert functional group” is a groupwhich does not substantially interfere with the process described hereinin which the material having an inert functional group takes part and/ordoes not complex with the metal compound of the metal complex. The term“does not complex with the metal compound” can include groups that couldcomplex with a metal compound but in particular molecules describedherein may not complex with a metal compound due to its positionalrelationship within a ligand. For example, while an ether group cancomplex with a metal compound, an ether group located at a para positionof a substituted phenyl phosphinyl group in a N²-phosphinyl amidine canbe an inert functional group because a single metal compound cannotcomplex with both the para ether group and the N²-phosphinyl amidinegroup in a single metal complex molecule. Thus, the inertness of aparticular functional group is not only related to the functionalgroup's inherent inability to complex the metal compound but can also berelated to the functional group's position within the metal complex.Non-limiting examples of inert functional groups which do notsubstantially interfere with processes described herein can include halo(fluoro, chloro, bromo, and iodo), nitro, hydrocarboxy groups (e.g.,alkoxy, and/or aroxy, among others), sulfidyl groups, and/or hydrocarbylgroups, among others.

The term “hydrocarbon” whenever used in this specification and claimsrefers to a compound containing only carbon and hydrogen. Otheridentifiers can be utilized to indicate the presence of particulargroups in the hydrocarbon (e.g. halogenated hydrocarbon indicates thatthe presence of one or more halogen atoms replacing an equivalent numberof hydrogen atoms in the hydrocarbon). The term “hydrocarbyl group” isused herein in accordance with the definition specified by IUPAC: aunivalent group formed by removing a hydrogen atom from a hydrocarbon.Similarly, a “hydrocarbylene group” refers to a group formed by removingtwo hydrogen atoms from a hydrocarbon, either two hydrogen atoms fromone carbon atom or one hydrogen atom from each of two different carbonatoms. Therefore, in accordance with the terminology used herein, a“hydrocarbon group” refers to a generalized group formed by removing oneor more hydrogen atoms (as necessary for the particular group) from ahydrocarbon. A “hydrocarbyl group,” “hydrocarbylene group,” and“hydrocarbon group” can be acyclic or cyclic groups, and/or can belinear or branched. A “hydrocarbyl group,” “hydrocarbylene group,” and“hydrocarbon group” can include rings, ring systems, aromatic rings, andaromatic ring systems, which contain only carbon and hydrogen.“Hydrocarbyl groups,” “hydrocarbylene groups,” and “hydrocarbon groups”include, by way of example, aryl, arylene, arene, alkyl, alkylene,alkane, cycloalkyl, cycloalkylene, cycloalkane, aralkyl, aralkylene, andaralkane groups, among other groups, as members.

The term “alkane” whenever used in this specification and claims refersto a saturated hydrocarbon compound. Other identifiers can be utilizedto indicate the presence of particular groups in the alkane (e.g.halogenated alkane indicates that the presence of one or more halogenatoms replacing an equivalent number of hydrogen atoms in the alkane).The term “alkyl group” is used herein in accordance with the definitionspecified by IUPAC: a univalent group formed by removing a hydrogen atomfrom an alkane. Similarly, an “alkylene group” refers to a group formedby removing two hydrogen atoms from an alkane (either two hydrogen atomsfrom one carbon atom or one hydrogen atom from two different carbonatoms). An “alkane group” is a general term that refers to a groupformed by removing one or more hydrogen atoms (as necessary for theparticular group) from an alkane. An “alkyl group,” “alkylene group,”and “alkane group” can be acyclic or cyclic groups, and/or can be linearor branched unless otherwise specified. Primary, secondary, and tertiaryalkyl groups are derived by removal of a hydrogen atom from a primary,secondary, or tertiary carbon atom, respectively, of an alkane. Then-alkyl group can be derived by removal of a hydrogen atom from aterminal carbon atom of a linear alkane.

An aliphatic compound is an acyclic or cyclic, saturated or unsaturatedcarbon compound, excluding aromatic compounds. Thus, an aliphaticcompound is an acyclic or cyclic, saturated or unsaturated carboncompound, excluding aromatic compounds; that is, an aliphatic compoundis a non-aromatic organic compound. An “aliphatic group” is ageneralized group formed by removing one or more hydrogen atoms (asnecessary for the particular group) from the carbon atom of an aliphaticcompound. Aliphatic compounds and therefore aliphatic groups can containorganic functional group(s) and/or atom(s) other than carbon andhydrogen.

The term “substituted” when used to describe a compound or group, forexample, when referring to a substituted analog of a particular compoundor group, is intended to describe any non-hydrogen moiety that formallyreplaces a hydrogen in that group, and is intended to be non-limiting. Agroup or groups can also be referred to herein as “unsubstituted” or byequivalent terms such as “non-substituted,” which refers to the originalgroup in which a non-hydrogen moiety does not replace a hydrogen withinthat group. “Substituted” is intended to be non-limiting and includeinorganic substituents or organic substituents.

The term “olefin” whenever used in this specification and claims refersto hydrocarbons that have at least one carbon-carbon double bond that isnot part of an aromatic ring or an aromatic ring system. The term“olefin” includes aliphatic and aromatic, cyclic and acyclic, and/orlinear and branched hydrocarbons having at least one carbon-carbondouble bond that is not part of an aromatic ring or ring system unlessspecifically stated otherwise. Olefins having only one, only two, onlythree, etc. . . . carbon-carbon double bonds can be identified by use ofthe term “mono,” “di,” “tri,” etc. . . . within the name of the olefin.The olefins can be further identified by the position of thecarbon-carbon double bond(s).

The term “alkene” whenever used in this specification and claims refersto a linear or branched aliphatic hydrocarbon olefin that has one ormore carbon-carbon double bonds. Alkenes having only one, only two, onlythree, etc. . . . such multiple bonds can be identified by use of theterm “mono,” “di,” “tri,” etc. . . . within the name. Alkenes can befurther identified by the position of the carbon-carbon double bond(s).Other identifiers can be utilized to indicate the presence or absence ofparticular groups within an alkene. For example, a haloalkene refers toan alkene having one or more hydrogen atoms replaced with a halogenatom.

The term “alpha olefin” as used in this specification and claims refersto an olefin that has a carbon-carbon double bond between the first andsecond carbon atoms of the longest contiguous chain of carbon atoms. Theterm “alpha olefin” includes linear and branched alpha olefins unlessexpressly stated otherwise. In the case of branched alpha olefins, abranch can be at the 2-position (a vinylidene) and/or the 3-position orhigher with respect to the olefin double bond. The term “vinylidene”whenever used in this specification and claims refers to an alpha olefinhaving a branch at the 2-position with respect to the olefin doublebond. By itself, the term “alpha olefin” does not indicate the presenceor absence of other carbon-carbon double bonds unless explicitlyindicated.

The term “normal alpha olefin” whenever used in this specification andclaims refers to a linear aliphatic mono-olefin having a carbon-carbondouble bond between the first and second carbon atoms. It is noted that“normal alpha olefin” is not synonymous with “linear alpha olefin” asthe term “linear alpha olefin” can include linear olefinic compoundshaving a double bond between the first and second carbon atoms andadditional double bonds.

The term “reaction zone effluent,” and it derivatives generally refersto all materials which exit the reaction zone through a reaction zoneoutlet which discharges a reaction mixture and can include reactionsystem feed(s) (e.g., ethylene, catalyst system or catalyst systemcomponents, and/or organic reaction medium), and/or reaction product(s)(e.g., oligomer product including oligomers and non-oligomers. The term“reaction zone effluent” and its derivatives can be qualified to referto certain portions by use of additional qualifying terms. For example,while reaction zone effluent refers to all material which exits thereaction system through the reaction zone outlet/discharge, a reactionzone oligomer product effluent refers to only the oligomer productwithin the reaction zone effluent.

The terms “room temperature” or “ambient temperature” are used herein todescribe any temperature from 15° C. to 35° C. wherein no external heator cooling source is directly applied to the reaction vessel.Accordingly, the terms “room temperature” and “ambient temperature”encompass the individual temperatures and any and all ranges, subranges,and combinations of subranges of temperatures from 15° C. to 35° C.wherein no external heating or cooling source is directly applied to thereaction vessel. The term “atmospheric pressure” is used herein todescribe an earth air pressure wherein no external pressure modifyingmeans is utilized. Generally, unless practiced at extreme earthaltitudes, “atmospheric pressure” is about 1 atmosphere (alternatively,about 14.7 psi or about 101 kPa).

Features within this disclosure that are provided as minimum values canbe alternatively stated as “at least” or “greater than or equal to” anyrecited minimum value for the feature disclosed herein. Features withinthis disclosure that are provided as maximum values can be alternativelystated as “less than or equal to” for the feature disclosed herein.

Within this disclosure the normal rules of organic nomenclature prevail.For instance, when referencing substituted compounds or groups,references to substitution patterns are taken to indicate that theindicated group(s) is (are) located at the indicated position and thatall other non-indicated positions are hydrogen. For example, referenceto a 4-substituted phenyl group indicates that there is a non-hydrogensubstituent located at the 4 position and hydrogens located at the 2, 3,5, and 6 positions. References to compounds or groups havingsubstitution at positions in addition to the indicated position can bereferenced using comprising or some other alternative language. Forexample a reference to a phenyl group comprising a substituent at the 4position refers to a phenyl group having a non-hydrogen substituentgroup at the 4 position and hydrogen or any non-hydrogen group at the 2,3, 5, and 6 positions.

Use of the term “optionally” with respect to any element of a claim isintended to mean that the subject element is required, or alternatively,is not required. Both alternatives are intended to be within the scopeof the claim.

Processes, systems, and/or reaction systems described herein can utilizesteps, features, compounds and/or equipment which are independentlydescribed herein. The process and/or methods described herein may or maynot utilize step identifiers (e.g., 1), 2), etc., a), b), etc., i), ii),etc., or first, second etc., among others), feature identifiers (e.g.,1), 2), etc., a), b), etc., i), ii), etc., or first, second etc., amongothers), and/or compound and/or composition identifiers (e.g., 1), 2),etc., a), b), etc., i), ii), etc., or first, second etc., among others).However, it should be noted that processes, systems, and/or reactionsystems described herein can have multiple steps, features (e.g. reagentratios, formation conditions, among other considerations), and/ormultiple compounds and/or composition using no descriptor or sometimeshaving the same general identifier. Consequently, it should be notedthat the processes, systems, and/or reaction systems methods describedherein can be modified to use an appropriate step or feature identifier(e.g., 1), 2), etc., a), b), etc., i), ii), etc., or first, second etc.,among others), feature identifier (e.g., 1), 2), etc., a), b), etc., i),ii), etc., or first, second etc., among others), and/or compoundidentifier (e.g., first, second, etc.) regardless of step, feature,and/or compound identifier utilized in the a particular aspect and/orembodiment described herein and that step or feature identifiers can beadded and/or modified to indicate individual differentsteps/features/compounds utilized within the process, systems, and/orreaction systems methods without detracting from the general disclosure.

Processes, systems, and/or reaction systems for forming ethyleneoligomer products are described herein. Such processes generallycomprise contacting ethylene and a catalyst system to form an ethyleneoligomer product under oligomerization conditions. As used herein, theterm “oligomerization” and its derivatives, refers to processes whichproduce a mixture of products containing at least 70 weight percentproducts containing from 2 to 30 ethylene units. Similarly, as usedherein, an “ethylene oligomer” is a product that contains from 2 to 30ethylene units while an “ethylene oligomer product” includes allproducts made by the process including the “ethylene oligomers” andproducts which are not “ethylene oligomers” (e.g., products whichcontain more than 30 monomer units). Further the terms “ethyleneoligomer product” and “ethylene oligomerization product” can be usedinterchangeably.

As used herein, the term “trimerization,” and it derivatives, refers toa process which produces a mixture of products containing at least 70weight percent products containing three and only three ethylene units.As used herein a “trimer” is a product which contains three and onlythree ethylene units while a “trimerization product” includes allproducts made by the trimerization process including trimer and productwhich are not trimers (e.g. dimers or tetramers). Generally, a“trimerization” process using ethylene produces an oligomer productcontaining at least 70 weight percent hexene(s).

As used herein, the term “tetramerization,” and its derivatives, refersto a process which produces a mixture of products containing at least 70weight percent products containing four and only four ethylene units. Asused herein a “tetramer” is a product which contains four and only fourethylene units while a “tetramerization product” includes all productsmade by the tetramerization process including tetramer and productswhich are not tetramers (e.g. dimers or trimer). Generally, a“tetramerization” process using ethylene produces an oligomer productcontaining at least 70 weight percent octene(s).

As used herein, the term “trimerization and tetramerization,” and itderivatives, refers to a process which produces an oligomer productcontaining at least 70 weight percent products containing three and/orfour and only three and/or four ethylene units. As used herein a“trimerization and tetramerization product” includes all products madeby the “trimerization and tetramerization” process including trimer,tetramer, and products which are not trimers or tetramers (e.g. dimers).Generally, a “trimerization and tetramerization” process using ethyleneproduces an oligomer product containing at least 70 weight percenthexene(s) and/or octene(s).

As used herein, mass and weight in any form (e.g., mass or weight, massratio or weight ratio) can be used interchangeably.

As used herein, the phrases “the C₃₊ olefin is not an ethylene oligomerformed in-situ within the reaction zone,” “the C₃₊ olefin and the C₃₊olefin of the reaction zone C₃₊ olefin:ethylene weight ratio is not anethylene oligomer formed in-situ within the reaction zone,” “the C₃₊olefin of the reaction zone and/or the C₃₊ olefin of the C₃₊ olefin toethylene reaction zone weight ratio is not an ethylene oligomer formedin-situ within the reaction zone,” and similar terms used herein, referto the C₃₊ olefin which is used in particular aspects and embodimentsdisclosed herein. In particular, these phases specifically indicate thatthe C₃₊ olefin to which they refer is not an ethylene oligomer formedin-situ within the reaction zone. That is to say that while the C₃₊olefin to which they refer can have the identity of an ethylene oligomerthat is formed in the reaction zone, the C₃₊ olefin to which they referwas not formed in the reaction as a consequence of the oligomerizationreaction the is occurring in the reaction zone. For example, an olefincomprising 1-hexene and/or 1-octene can be added to the reaction whichis producing 1-hexene and/or 1-octene, however, since the 1-hexeneand/or 1-octene was added to the reaction, it is not an ethyleneoligomer produced in-situ within the reaction zone and thus would beconsidered in the noted phrases while the 1-hexene and/or 1-octeneproduce in-situ within the reaction zone would not be not considered inthe noted phrases.

Various aspects and embodiments described herein may refer to asubstituted group or compound. In an embodiment, each substituent of anyaspect or embodiment calling for a substituent can be a halogen, ahydrocarbyl group, or a hydrocarboxy group; alternatively, a halogen ora hydrocarbyl group; alternatively, a halogen or a hydrocarboxy group;alternatively, a hydrocarbyl group or a hydrocarboxy group;alternatively, a halogen; alternatively, a hydrocarbyl group; oralternatively, a hydrocarboxy group. In an embodiment, each hydrocarbylsubstituent can be a C₁ to C₁₀ hydrocarbyl group; or alternatively, a C₁to C₅ hydrocarbyl group. In an embodiment, each hydrocarboxy group canbe a C₁ to C₁₀ hydrocarboxy group; or alternatively, a C₁ to C₅hydrocarboxy group.

In an embodiment, any halide substituent of any aspect or embodimentcalling for a substituent can be a fluoride, chloride, bromide, oriodide; alternatively, a fluoride or chloride. In some embodiments, anyhalide substituent of any aspect or embodiment calling for a substituentcan be a fluoride; alternatively, a chloride; alternatively, a bromide;or alternatively, an iodide.

In an embodiment, any hydrocarbyl substituent of any aspect orembodiment calling for a substituent can be an alkyl group, an arylgroup, or an aralkyl group; alternatively, an alkyl group;alternatively, an aryl group; or alternatively, an aralkyl group. In anembodiment, any alkyl substituent of any aspect or embodiment callingfor a substituent can be a methyl group, an ethyl group, an n-propylgroup, an isopropyl group, an n-butyl group, a sec-butyl group, anisobutyl group, a tert-butyl group, an n-pentyl group, a 2-pentyl group,a 3-pentyl group, a 2-methyl-1-butyl group, a tert-pentyl group, a3-methyl-1-butyl group, a 3-methyl-2-butyl group, or a neo-pentyl group;alternatively, a methyl group, an ethyl group, an isopropyl group, atert-butyl group, or a neo-pentyl group; alternatively, a methyl group;alternatively, an ethyl group; alternatively, an isopropyl group;alternatively, a tert-butyl group; or alternatively, a neo-pentyl group.In an embodiment, any aryl substituent of any aspect or embodimentcalling for a substituent can be phenyl group, a tolyl group, a xylylgroup, or a 2,4,6-trimethylphenyl group; alternatively, a phenyl group;alternatively, a tolyl group, alternatively, a xylyl group; oralternatively, a 2,4,6-trimethylphenyl group. In an embodiment, anyaralkyl substituent of any aspect or embodiment calling for asubstituent can be benzyl group or an ethylphenyl group(2-phenyleth-1-yl or 1-phenyleth-1-yl); alternatively, a benzyl group;alternatively, an ethylphenyl group; alternatively a 2-phenyleth-1-ylgroup; or alternatively, a 1-phenyleth-1-yl group.

In an embodiment, any hydrocarboxy substituent of any aspect orembodiment calling for a substituent can be an alkoxy group, an aryloxygroup, or an aralkoxy group; alternatively, an alkoxy group;alternatively, an aryloxy group, or an aralkoxy group. In an embodiment,any alkoxy substituent of any aspect or embodiment calling for asubstituent can be a methoxy group, an ethoxy group, an n-propoxy group,an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxygroup, a tert-butoxy group, an n-pentoxy group, a 2-pentoxy group, a3-pentoxy group, a 2-methyl-1-butoxy group, a tert-pentoxy group, a3-methyl-1-butoxy group, a 3-methyl-2-butoxy group, or a neo-pentoxygroup; alternatively, a methoxy group, an ethoxy group, an isopropoxygroup, a tert-butoxy group, or a neo-pentoxy group; alternatively, amethoxy group; alternatively, an ethoxy group; alternatively, anisopropoxy group; alternatively, a tert-butoxy group; or alternatively,a neo-pentoxy group. In an embodiment, any aryloxy substituent of anyaspect or embodiment calling for a substituent can be phenoxy group, atoloxy group, a xyloxy group, or a 2,4,6-trimethylphenoxy group;alternatively, a phenoxy group; alternatively, a toloxy group,alternatively, a xyloxy group; or alternatively, a2,4,6-trimethylphenoxy group. In an embodiment, any aralkoxy substituentof any aspect or embodiment calling for a substituent can be benzoxygroup.

Aspects disclosed herein can provide the materials listed as suitablefor satisfying a particular feature of the embodiment delimited by theterm “or.” For example, a particular feature of the disclosed subjectmatter can be disclosed as follows: Feature X can be A, B, or C. It isalso contemplated that for each feature the statement can also bephrased as a listing of alternatives such that the statement “Feature Xis A, alternatively B, or alternatively C” is also an embodiment of thepresent disclosure whether or not the statement is explicitly recited.

Disclosed herein are processes, systems, and reactions systems for theoligomerization of ethylene to form an ethylene oligomer productcomprising normal linear alpha olefins (NAO). In particular, processes,systems, and/or reaction systems described herein can selectivelytrimerize, tetramerize, or trimerize and tetramerize ethylene to producean ethylene oligomer product containing hexenes (e.g.,1-hexene) and/oroctenes (e.g.,1-octene). It has been unexpectedly found that theselective ethylene oligomerization processes, systems, and/or reactionsystems using the catalyst systems disclosed herein are sensitive tospecific reactor feed conditions. It has been unexpectedly found thatlarge amounts of polymer can form during the startup of the reactionzone of a selective ethylene oligomerization. This polymer formation candecrease as reaction zone on stream time increases. Particularly, andwhile not wishing to be bound by theory, it is believed that in theabsence of a significant amount of C₃₊ olefin the catalyst systemsdisclosed herein can have a greater propensity to produced polymer andthus during a reaction zone startup when very little olefin is presentthe catalyst system can produce a large amount of polymer. It has beendiscovered that the presence of a C₃₊ olefin during the initial phase ofselective ethylene oligomerization (e.g., during the startup of aselective ethylene oligomerization reaction zone) can reduce that amountof polymer formed and can lead to the improved operation of processes,systems, and/or reaction systems for selective ethyleneoligomerizations. It has also believed, without being limited by theory,that polymer can form with use of the herein disclosed selectiveoligomerization catalyst systems when concentrated portions of ethyleneare contacted with a catalyst system. Thus, the contacting of a highconcentration of ethylene with the selective ethylene oligomerizationcatalyst system can be another situation which can make polymer pluggingand/or fouling of reaction zone components a limiting factor in oligomerproduction. In this later situation, it has been discovered thatcontacting (or diluting) the ethylene with an organic reaction mediumprior to contacting ethylene with the catalyst system can reduce polymerformation when compared to contacting a high concentration of ethylenewith the catalyst system and provide improved operation of processes,systems, and/or reaction systems. Further it has be found that 1) thepresence of a C₃₊ olefin during the startup of a selective ethyleneoligomerization and 2) the contacting (or diluting) the ethylene withorganic reaction medium prior to the contact of the ethylene with thecatalyst systems either during the startup of an selective ethyleneoligomerization, after the startup of a selective ethyleneoligomerization, or both can lead to improved operation of processes,systems, and/or reaction systems for selective ethyleneoligomerizations. The disclosed processes, systems, and/or reactionsystems can reduce the amount of polymer formed 1) during startup of aselective ethylene oligomerization reaction, 2) reduce the amount ofpolymer formed during normal operation of a selective ethyleneoligomerization reaction, and/or 3) increases hexenes and/or octenesproductivity and/or production and thus avoid fouling and/or plugging ofthe reaction zone and/or reaction system components.

The disclosed processes, systems, and/or reaction systems (e.g., thoseillustrated in FIGS. 1 to 3) can comprise a) contacting i) ethylene, ii)a catalyst system comprising (a) a chromium component comprising achromium compound, (b) a heteroatomic ligand, and (c) an aluminoxane (oralternatively, (a) a chromium component comprising a chromium compoundheteroatomic ligand complex, and (b) an aluminoxane), iii) an organicreaction medium, and iv) optionally hydrogen; and forming an ethyleneoligomer product in a reaction zone. In an embodiment, a C₃₊ olefin canbe present in the reaction zone of the disclosed processes, systems,and/or reaction systems for a period of time, where the C₃₊ olefin isnot an ethylene oligomer formed in-situ within the reaction zone. In acombinable embodiment of the processes, systems, and/or reaction systemsdisclosed herein, the reaction zone can have a C₃₊ olefin to ethylenereaction zone weight ratio that over a period of time decreases from atleast an initial value (any disclosed herein) to less than a final value(any disclosed herein). In an embodiment of the processes, systems,and/or reaction systems disclosed herein, the period of time can beinitiated at a point in time when the reaction zone is not producingethylene oligomer product and/or when the flow rate of ethylene is zero.

A disclosed process can comprise a) introducing into a reaction zonecontaining a C₃₊ olefin and optionally an organic reaction mediumwherein the reaction zone can be substantially devoid of ethylene; i)ethylene ii) a catalyst system comprising (a) a chromium componentcomprising a chromium compound, (b) a heteroatomic ligand, and (c) analuminoxane (or alternatively, a catalyst system comprising (a) achromium component comprising a heteroatomic ligand chromium compoundcomplex (any described herein), and (b) an aluminoxane (any disclosedherein), iii) the organic reaction medium, and iv) optionally hydrogen;and b) forming an ethylene oligomer product in the reaction zone. In anembodiment of this process, the C₃₊ olefin is not an ethylene oligomerformed in-situ within the reaction zone. In a combinable embodiment ofthis process, the reaction zone can have a C₃₊ olefin to ethylene zonemass ratio that over a period of time decreases from at least an initialvalue (any disclosed herein) to less than a final value (any disclosedherein).

A disclosed process or system can comprise a) contacting in a reactionzone i) a C₃₊ olefin, ii) ethylene, iii) a catalyst system comprising(a) a chromium component comprising a chromium compound (any describedherein), (b) a heteroatomic ligand, and (c) an aluminoxane (anydisclosed herein) (or alternatively, a catalyst system comprising (a) achromium component comprising a heteroatomic ligand chromium compoundcomplex, and (b) an aluminoxane), iv) an organic reaction medium, and v)optionally hydrogen into the reaction zone; and c) forming an ethyleneoligomer product.

Another disclosed process can comprise a) contacting i) ethylene, ii) acatalyst system comprising (a) a chromium component comprising achromium compound, (b) a heteroatomic ligand, and (c) an aluminoxane (oralternatively, a catalyst system comprising (a) a chromium componentcomprising a heteroatomic ligand chromium compound complex, and (b) analuminoxane), iii) an organic reaction medium, and iv) optionallyhydrogen in a reaction zone; b) forming an ethylene oligomer product inthe reaction zone; wherein ethylene, the catalyst system, and theorganic reaction medium are introduced into the reaction zone and for aperiod of time a C₃₊ olefin is introduced into the reaction zone. In anembodiment, ethylene, the organic reaction medium, and for the period oftime the C₃₊ olefin can be separately introduced into the reaction zone;alternatively, ethylene and at least a portion of the organic reactionmedium can be contacted to form a feedstock mixture prior to theethylene contacting the catalyst system and the feedstock mixture can beintroduced into the reaction zone, and for the period of time the C₃₊olefin can be separately introduced to the reaction zone; oralternatively, ethylene, at least a portion of the organic reactionmedium, and for the period of time the C₃₊ olefin can be contacted toform a feedstock mixture prior to the ethylene contacting the catalystsystem and the feedstock mixture introduced into the reaction zone. Whenthe ethylene and the C₃₊ olefin are separately introduced into thereaction zone, the processes can further comprise introducing the C₃₊olefin to the reaction zone prior to introducing the ethylene, thecatalyst system, or both the ethylene and the catalyst system to thereaction zone. In an embodiment, the reaction zone can have a C₃₊olefin:ethylene weight ratio that over a period of time decreases fromat least an initial value (any disclosed herein) to less than a finalvalue (any disclosed herein) and wherein the C₃₊ olefin and the C₃₊olefin of the reaction zone C₃₊ olefin:ethylene weight ratio is not anethylene oligomer formed in-situ within the reaction zone.

A disclosed process can comprise a) feeding a catalyst system to areaction zone, the catalyst system comprising i) a chromium componentcomprising a chromium compound, ii) a heteroatomic ligand, and iii) analuminoxane (or alternatively, a catalyst system comprising i) achromium component comprising a heteroatomic ligand chromium compoundcomplex, and ii) an aluminoxane); b) for a period of time separatelyfeeding to the reaction zone a feedstock mixture comprising ethylene andi) a C₃₊ olefin, and ii) at least a portion of an organic reactionmedium, or iii) combinations of i) and ii); wherein the feedstockmixture is substantially free of the catalyst system; c) contacting thecatalyst system and the feedstock mixture in the reaction zone; and d)forming an ethylene oligomer product in the reaction zone. Anotherdisclosed process can comprise a) contacting i) ethylene, at least aportion of an organic reaction medium, and for a period of time a C₃₊olefin to form a feedstock mixture; b) subsequent to a), contacting in areaction zone the feedstock mixture with a catalyst system comprising i)a chromium component comprising a chromium compound, ii) a heteroatomicligand, and iii) an aluminoxane (or alternatively, a catalyst systemcomprising i) a chromium component comprising a heteroatomic ligandchromium compound complex, and ii) an aluminoxane); and c) forming anethylene oligomer product in the reaction zone. A further disclosedprocess can comprise a) diluting ethylene by addition of i) at least aportion of an organic reaction medium, ii) for a period of time a C₃₊olefin, or iii) for a period of time at least a portion of an organicreaction medium and C₃₊ olefin to form a feedstock mixture prior tocontacting the ethylene with a catalyst system in a reaction zone; b)contacting in the reaction zone the feedstock mixture and the catalystsystem, wherein the catalyst system comprises i) a chromium componentcomprising a chromium compound, ii) a heteroatomic ligand, and iii) analuminoxane (alternatively, a catalyst system comprising i) a chromiumcomponent comprising a heteroatomic ligand chromium compound complex,and ii) an aluminoxane); and c) forming an ethylene oligomer product inthe reaction zone. A disclosed system can comprise: a) a feedstockmixture comprising ethylene, an organic reaction medium, and for aperiod of time a C₃₊ olefin; b) a catalyst system comprising i) achromium component comprising a chromium compound, ii) a heteroatomicligand, and iii) an aluminoxane (or alternatively, a catalyst systemcomprising i) a chromium component comprising a heteroatomic ligandchromium compound complex, and ii) an aluminoxane; and c) a reactionzone receiving the feedstock mixture separately from the catalyststream. In an embodiment, the system can further comprise a reactionzone effluent line comprising an ethylene oligomer product formed in thereaction zone. In some embodiments of the processes and systems, 1) theC₃₊ olefin can be dispersed in the feedstock mixture, for a period oftime, prior to introducing/feeding the feedstock mixture into thereaction zone and/or 2) ethylene can be dispersed within the feedstockmixture prior to ethylene contacting the catalyst system. In anothercombinable embodiment of the processes and systems, ethylene can bedispersed within the feedstock mixture prior to introduction of thefeedstock mixture into the reaction zone. In an embodiment of theprocesses and systems, the period of time can occur during a reactionzone startup.

A disclosed process can comprise a) feeding a catalyst system to areaction zone, the catalyst system comprising i) a chromium componentcomprising a chromium compound, ii) a heteroatomic ligand, and iii) analuminoxane (or alternatively, a catalyst system comprising i) achromium component comprising a heteroatomic ligand chromium compoundcomplex, and ii) an aluminoxane); b) separately feeding to the reactionzone a feedstock mixture comprising i) ethylene, ii) an organic reactionmedium, and iii) for a period of time a C₃₊ olefin to contact thecatalyst system. In an embodiment, the period of time can occur during areaction zone startup. Another disclosed process can comprise a startupof a reaction zone, where the process can comprise for a period of timecontacting in the reaction zone 1) ethylene, 2) a catalyst systemcomprising a) a chromium component comprising a chromium compound, b) aheteroatomic ligand, and c) an aluminoxane (or alternatively, a catalystsystem comprising a) a chromium component comprising a heteroatomicligand chromium compound complex) and b) an aluminoxane), 3) an organicreaction medium, and 4) optionally hydrogen to form an ethylene oligomerproduct; wherein: the catalyst system can be introduced/fed to thereaction zone in a feedstock mixture comprising i) ethylene, ii) atleast a portion of the organic reaction medium, and iii) for a period oftime a C₃₊ olefin is introduce/fed to the reaction zone, wherein thefeedstock mixture is substantially free of the catalyst system prior tothe feedstock mixture contacting the catalyst system in the reactionzone. In an embodiment of these processes, for the period of time theC₃₊ olefin is part of the feedstock mixture introduced/fed to thereaction zone, the C₃₊ olefin can be dispersed the feedstock mixtureprior to introducing/feeding the feedstock mixture into the reactionzone and/or ethylene can be dispersed within the feedstock mixture priorto ethylene contacting the catalyst system.

A disclosed reaction system can comprise a reaction zone; a firstreaction zone inlet configured to introduce a catalyst system comprising(a) a chromium component comprising a chromium compound, (b) aheteroatomic ligand, and (c) an aluminoxane (or alternatively, acatalyst system comprising (a) a chromium component comprising aheteroatomic ligand chromium compound complex, and (b) an aluminoxane)to the reaction zone; a second reaction zone inlet configured tointroduce ethylene, an organic reaction medium, and optionally hydrogento the reaction zone; a C₃₊ olefin feed line in fluid communication withthe first reaction zone inlet, the second reaction zone inlet, or athird reaction zone inlet configured to introduce a C₃₊ olefin to thereaction zone; and one or more reaction zone outlets configured todischarge the reaction zone effluent comprising an ethylene oligomerproduct from the reaction zone. In an embodiment, the reaction systemcan further comprise a catalyst system feed line flowing the catalystsystem to the first reaction zone inlet; an ethylene feed linecomprising the ethylene; an organic reaction medium feed line comprisingthe organic reaction medium, wherein the organic reaction medium feedline and the ethylene feed line can combine to yield a feedstock mixturewhich can introduced to the reaction zone via the second reaction zoneinlet, wherein the C₃₊ olefin feed line can combine with at least one ofthe catalyst system feed line, the ethylene feed line, the organicreaction medium feed line, the feedstock mixture feed line, or adispersed feedstock mixture feed line formed by passing the feedstockmixture through a mixing device prior to flowing to the reaction zonevia the second reaction zone inlet. In a combinable embodiment, thereaction system can further comprise a pump in fluid communication withthe second reaction zone inlet and can be located upstream of a pointwhere the ethylene feed line and the organic reaction medium feed linejoin to produce the feedstock mixture; and a mixing device positionedbetween i) the joining of the ethylene feed line and the organicreaction medium feed line and ii) the second reaction zone inlet todisperse the ethylene and the organic reaction medium prior to thefeedstock mixture entering the reaction zone. In another combinablereaction system embodiment, during steady state operation the firstreaction zone inlet can be configured to periodically or continuouslyintroduce the catalyst system to the reaction zone, the second reactionzone inlet can be configured to periodically or continuously introducedthe feedstock mixture to the reaction zone, and the one or more reactionzone outlets can be configured to periodically or continuously dischargethe reaction zone effluent from the reaction zone.

Another disclosed reaction system can comprise a reaction zone; areaction zone inlet configured to introduce a catalyst system, ethylene,an organic reaction medium, and a C₃₊ olefin to the reaction zone; anethylene feed line comprising ethylene, a C₃₊ olefin feed linecomprising a C₃₊ olefin, an organic reaction medium feed line comprisingan organic reaction medium and optionally a hydrogen feed linecomprising hydrogen all in fluid communication with the reaction zoneinlet, wherein the organic reaction medium feed line can combine withthe ethylene feed line to form a feedstock mixture feed line in fluidcommunication with the reaction zone inlet; a catalyst system feed linecomprising the catalyst system in fluid communication with the reactionzone inlet, wherein the catalyst system feed line combines with theethylene feed line, the organic reaction medium feed line, the feedstockmixture feed line, or a dispersed feedstock mixture feed line formed bypassing the feedstock mixture feed line through a mixing device; one ormore reaction zone outlets configured to discharge the reaction zoneeffluent comprising an ethylene oligomer product from the reaction zone,wherein the catalyst system comprises (a) a chromium componentcomprising a chromium compound, (b) a heteroatomic ligand, and (c) analuminoxane (or alternatively, a catalyst system comprising (a) achromium component comprising a heteroatomic ligand chromium compoundcomplex, and (b) an aluminoxane), and wherein the C₃₊ olefin feed linecan join with one or more of the ethylene feed line, the organicreaction medium feed line, the feedstock mixture feed line, thedispersed feedstock mixture feed line, or a combined feed line formed byjoining the catalyst system feed line and the dispersed feedstockmixture feed line. In an embodiment, the reaction system can furthercomprise a mixing device positioned between i) the joining of theethylene feed line and the organic reaction medium feed line and ii) thereaction zone inlet to disperse the ethylene within the feedstockmixture prior to the feedstock mixture joining with the catalyst systemand entering the reaction zone. In a combinable embodiment, the reactionzone inlet can be configured to periodically or continuously introducethe catalyst system and the feedstock mixture to the reaction zone, andthe one or more reaction zone outlets can be configured to periodicallyor continuously discharge the reaction zone effluent from the reactionzone.

A further disclosed reaction system can comprise a reaction zone; afirst reaction zone inlet configured to introduce a catalyst systemcomprising (a) a chromium component comprising a chromium compound, (b)a heteroatomic ligand, and (c) an aluminoxane (or alternatively, acatalyst system comprising (a) a chromium component comprising aheteroatomic ligand chromium compound complex, and (b) an aluminoxane)to the reaction zone; a second reaction zone inlet configured tointroduce ethylene and optionally hydrogen to the reaction zone; a thirdreaction zone inlet configured to introduce an organic reaction mediumto the reaction zone; a C₃₊ olefin feed line in fluid communication withone or more of the first reaction zone inlet, the second reaction zoneinlet, the third reaction zone inlet, or a fourth reaction zone inletwhich is configured to introduce the C₃₊ olefin directly to the reactionzone; and one or more reaction zone outlets configured to discharge thereaction zone effluent comprising an ethylene oligomer product from thereaction zone. In an embodiment, the reaction system can furthercomprise a catalyst system feed line flowing the catalyst system to thefirst reaction zone inlet; an ethylene feed line flowing ethylene to thesecond reaction zone inlet; and an organic reaction medium feed lineflowing the organic reaction medium to the third reaction zone inlet,wherein the C₃₊ olefin feed line i) can combine with at least one of thecatalyst system feed line, the ethylene feed line, or the organicreaction medium feed line, or ii) can flow directly to the fourthreaction zone inlet.

In an embodiment, the processes, systems, and/or reaction systemdisclosed herein can further comprise, removing/withdrawing a reactionzone effluent comprising an ethylene oligomer product from the reactionzone. In an embodiment, the processes, systems, and/or reactions systemsdisclosed herein can be continuous processes, systems, and/or reactionsystems wherein the feeds (e.g., ethylene, catalyst system or catalystsystem components, organic reaction medium, C₃₊ (where applicable in theprocesses, systems, and/or reaction systems), and any other feeds can beperiodically or continuously introduced/fed to the reaction zone and areaction zone effluent comprising the ethylene oligomer product can beperiodically or continuously removed/withdrawn from the reaction zone.

In an embodiment of the processes, systems, and/or reaction systemdisclosed herein, the reaction zone can have a C₃₊ olefin to ethylenereaction zone mass ratio that over a period of time can decrease; oralternatively, have a C₃₊ olefin:ethylene weight ratio fed/introduced tothe reaction zone that over a period of time can decrease from at leastan initial value (any disclosed herein) to less than a final value (anydisclosed herein). Generally, the C₃₊ olefin of the reaction zone and/orthe C₃₊ olefin of the C₃₊ olefin to ethylene reaction zone mass ratio isnot an ethylene oligomer formed in-situ within the reaction zone. In acombinable embodiment, the applicable processes, systems, and/orreaction system disclosed herein can have ethylene and the C₃₊ olefinfed/introduced to the reaction zone (either separately, together in afeedstock mixture, or both) wherein a C₃₊ olefin:ethylene weight ratiofed/introduced to the reaction zone can decrease; or alternatively,decrease from at least an initial value to less than a final value overa period of time. In further combinable embodiment, the C₃₊ olefin toethylene reaction zone mass ratio and/or the C₃₊ olefin:ethylene weightratio fed/introduced to the reaction zone can decreases in steps; oralternatively, can decrease periodically or continuously.

Generally, the catalyst system, the catalyst system components (e.g.,the chromium component, the aluminoxane, among others), the organicreaction medium, the ethylene oligomer product, the conditions at whichthe ethylene oligomer product can be formed (or the reaction zone canoperate), the C₃₊ olefin, the reaction zone, a reaction zone C₃₊olefin:ethylene weight ratio, a reaction zone period of time, afeedstock mixture C₃₊ olefin:ethylene weight ratio, a feedstock mixtureperiod of time, an ethylene to organic reaction medium mass ratio, an(ethylene+C₃₊ olefin) to organic reaction medium mass ratio, componentsof the reaction system, and any other features disclosed herein for theprocesses, systems, and/or reaction system disclosed herein areindependently described herein. Additionally, further steps that can beutilized in the processes, systems, and/or reaction system areindependently disclosed herein. These independent descriptions can beutilized without limitation, and in any combination, to further describethe processes, systems, and/or reaction systems disclosed herein. Inparticular these independent descriptions can be utilized withoutlimitation, and in any combination, to further describe the processes,systems, and/or reaction systems where for a period of time a C₃₊ olefinwhich is not an ethylene oligomer formed in-situ within the reactionzone, is present in the reaction zone.

During the reaction zone period of time a C₃₊ olefin:ethylene weightratio in the reaction zone can decrease from at least an initial valueto less than a final value. In an embodiment, the reaction zone C₃₊olefin:ethylene weight ratio at least initial value independently can beany at least initial value disclosed herein and the reaction zone C₃₊olefin:ethylene weight ratio less than final value independently can beany less than final value disclosed herein. In an embodiment, thereaction zone C₃₊ olefin:ethylene weight ratio at least initial valuecan be a value of at least 0.5:1, 0.75:1, 1:1, 1.5:1, 2:1, 3:1, 5:1,10:1, 25:1, 50:1, or 100:1. In an embodiment, the reaction zone C₃₊olefin:ethylene weight ratio less than final value can be a value lessthan 0.2:1, 0.15:1, 0.1:1, 0.08:1, 0.06:1, 0.04:1, 0.02:1, or 0.01:1. Inan embodiment, the reaction zone C₃₊ olefin:ethylene weight ratio candecrease from any reaction zone C₃₊ olefin:ethylene weight ratio greaterthan initial value disclosed herein to any reaction zone C₃₊olefin:ethylene weight ratio less than final value disclosed herein.Thus, in some non-limiting embodiments, the reaction zone C₃₊olefin:ethylene weight ratio can decrease from at least 0.5:1 to lessthan 0.2:1, from at least 1:1 to less than 0.2:1, from at least 2:1 toless than 0.15:1, from at least 3:1 to less than 0.1:1, from at least5:1 to less than 0.15:1, from at least 10:1 to less than 0.2:1, from avalue of at least 100:1 to less than 0.1:1. Other embodiments, for whichthe reaction zone C₃₊ olefin:ethylene weight ratio can decrease from areaction zone C₃₊ olefin:ethylene weight ratio initial value to areaction zone C₃₊ olefin:ethylene weight ratio final value are readilyapparent to those skilled in the art with the aid of this disclosure. Inan embodiment, the reaction zone period of time can begin when thereaction zone C₃₊ olefin:ethylene weight ratio falls below the reactionzone C₃₊ olefin:ethylene weight ratio greater than initial value. In anembodiment, the reaction zone period of time can end when the reactionzone C₃₊ olefin:ethylene weight ratio falls below the less than finalvalue. In an embodiment, the reaction zone period of time can begin whenthe reaction zone is not producing ethylene oligomer product and/or whenthe flow rate of ethylene to the reaction zone is zero. In anembodiment, the reaction zone period of time can encompass a time wherethe reaction zone C₃₊ olefin:ethylene weight ratio decreases from about1:0 to about 0:1. In an embodiment, the reaction zone period of timerepresents the startup of the reaction zone.

In any embodiment wherein ethylene and the C₃₊ olefin are fed/introducedto the reaction zone (either separately, together in a feedstockmixture, or both), a C₃₊ olefin:ethylene weight ratio fed/introduced(either separately, together in a feedstock mixture, or both) to thereaction zone can decrease from at least an initial value to less than afinal value over a period of time. In an embodiment, the at leastinitial value of the C₃₊ olefin:ethylene weight ratio fed/introduced tothe reaction zone independently can be any at least initial valuedisclosed herein and the less than final value of the C₃₊olefin:ethylene weight ratio fed/introduced to the reaction zoneindependently can be any less than final value disclosed herein. In anembodiment, the at least initial value can be a value of at least 0.5:1,0.75:1, 1:1, 1.5:1, 2:1, 3:1, 5:1, 10:1, 25:1, 50:1, or 100:1. In anembodiment, the less than final value can be a value less than 0.2:1,0.15:1, 0.1:1, 0.08:1, 0.06:1, 0.04:1, 0.02:1, or 0.01:1. In anembodiment, the C₃₊ olefin:ethylene weight ratio can decrease from anygreater than initial value disclosed herein to any less than final valuedisclosed herein. Thus, in some non-limiting embodiments, the C₃₊olefin:ethylene weight ratio fed/introduced to the reaction zone candecrease from at least 0.5:1 to less than 0.2:1, from at least 1:1 toless than 0.2:1, from at least 2:1 to less than 0.15:1, from at least3:1 to less than 0.1:1, from at least 5:1 to less than 0.15:1, from atleast 10:1 to less than 0.2:1, from a value of at least 100:1 to lessthan 0.1:1. Other embodiments for which the C₃₊ olefin:ethylene weightratio fed/introduced to the reaction zone can decrease from an initialvalue to a final value are readily apparent to those skilled in the artwith the aid of this disclosure. In an embodiment wherein ethylene andthe C₃₊ olefin are fed/introduced to the reaction zone, the period oftime can begin when the C3+ olefin:ethylene weight ratio falls below thegreater than initial value. In an embodiment wherein ethylene and theC₃₊ olefin are fed/introduced to the reaction zone, the period of timecan end when the feedstock mixture C₃₊ olefin:ethylene weight ratiofalls below the less than final value. In another embodiment whereinethylene and the C₃₊ olefin are fed/introduced to the reaction zone, theperiod of time can begin when the feedstock mixture has an initial C₃₊olefin:ethylene weight ratio of about 1:0; or alternatively, the flowrate of ethylene is about zero. In an embodiment wherein ethylene andthe C₃₊ olefin are fed/introduced to the reaction zone, the period oftime can end when the feedstock mixture has a C₃₊ olefin:ethylene weightratio of about 0:1; or alternatively, the flow rate of the C₃₊ olefin isabout 0. In an embodiment wherein ethylene and the C₃₊ olefin arefed/introduced to the reaction zone, the period of time can encompass atime where the feedstock mixture C₃₊ olefin:ethylene weight ratiodecreases from about 1:0 to about 0:1. In an embodiment wherein ethyleneand the C₃₊ olefin are fed/introduced to the reaction zone, the periodof time can occur during the startup of the reaction zone.

In an embodiment, the reaction zone period of time and/or the C₃₊olefin/ethylene feed period of time over which the C₃₊ olefin:ethyleneweight ratio can decrease (e.g., from any at least initial valuedisclosed herein to any less than final value described herein) canprovide a benefit to the ethylene oligomerization processes, systems,and/or reaction systems described herein (e.g., a decrease in polymerproduction among other benefits described herein). In an embodiment, thereaction zone period of time and/or the C₃₊ olefin/ethylene feed periodof time over which the C₃₊ olefin:ethylene weight ratio can decrease canbe greater than or equal to 5, 10, 15, 20, 25, or 30 minutes;alternatively or additionally less than or equal to 6, 4, 3, 2, 1.5, or1 hour. In an embodiment, the reaction zone period of time and/or theC₃₊ olefin/ethylene feed period of time over which the C₃₊olefin:ethylene weight ratio can decrease can range from any greaterthan or equal to value described herein to any less than or equal todescribed herein. In some non-limiting embodiments, the reaction zoneperiod of time and/or the C₃₊ olefin/ethylene feed period of time overwhich the C₃₊ olefin:ethylene weight ratio can decrease can range fromgreater than or equal to 5 minutes to less than or equal to 6 hours;alternatively, greater than or equal to 10 minutes to less than or equalto 4 hours; alternatively, greater than or equal to 15 minutes to lessthan or equal to 4 hours; alternatively, greater than or equal to 20minutes to less than or equal to 3 hours; alternatively, greater than orequal to 25 minutes to less than or equal to 3 hours; alternatively,greater than or equal to 30 minutes to less than or equal to 3 hours;alternatively, greater than or equal to 30 minutes to less than or equalto 2 hours; or alternatively, greater than or equal to 30 minutes toless than or equal to 1.5 hours. Other ranges over which the reactionzone period of time and/or the C₃₊ olefin/ethylene feed period of timeover which the C₃₊ olefin:ethylene weight ratio can decrease are readilyapparent to those skilled in the art with the aid of this disclosure.Additionally, multiple periods of time over which the reaction zoneperiod of time and/or the C₃₊ olefin/ethylene feed period of time overwhich the C₃₊ olefin:ethylene weight ratio can decrease can be utilizedand these multiple periode of time can have the same duration; oralternatively, at least one of the multiple periods of time can have aduration which is different from the duration of at least another of themultiple periods of time.

The reaction zone period of time and the C₃₊ olefin/ethylene feed periodof time over which the C₃₊ olefin:ethylene weight ratio can decrease canoccur over the same time, e.g., simultaneously. Alternatively, a portionof the reaction zone period of time can overlap a portion of the C₃₊olefin/ethylene feed period of time. For example, the reaction zoneperiod of time can lag behind the C₃₊ olefin/ethylene feed period oftime period since, due to residence time consideration for the reactionzone 110, there will be a lag in time between when a decrease in the C₃₊olefin:ethylene weight ratio can be observed in the feed to the reactionzone 110 and when a decrease in the C₃₊ olefin:ethylene weight ratio canbe observed in the reaction zone 110 itself. Alternatively, the reactionzone period of time and the C₃₊ olefin/ethylene feed period of time donot overlap. For example, the lag in time between when a decrease in theC₃₊ olefin:ethylene weight ratio can be observed in the feed to thereaction zone 110 and when a decrease in the C₃₊ olefin:ethylene weightratio can be observed in the reaction zone 110 itself may be long enoughthat the periods of time (e.g., the reaction zone period of time and theC₃₊ olefin/ethylene feed period of time) occur sequentially or in series(over time).

In any embodiment wherein ethylene and the C₃₊ olefin are fed/introducedto the reaction zone (either separately, together in a feedstockmixture, or both), ethylene, the C₃₊ olefin, or both can be contactedwith the organic reaction medium (e.g., at least a portion of theorganic reaction medium) prior to contacting the catalyst system. Inother embodiments, the ethylene, the C₃₊ olefin, or both can bedispersed with the organic reaction medium (e.g., at least a portion ofthe organic reaction medium) prior to contacting the catalyst system.

In an embodiment wherein the feedstock mixture comprises ethylene andthe organic reaction medium (e.g., at least a portion of the organicreaction medium), ethylene and organic reaction medium can be contactedprior to ethylene contacting the catalyst system. In an embodiment,ethylene can be dispersed in the organic reaction medium (e.g., at leasta portion of the organic reaction medium) prior to ethylene contactingthe catalyst system. In some embodiments, ethylene and the organicreaction medium can be contacted, and/or the ethylene can be dispersedin the organic reaction medium prior to ethylene contacting the catalystsystem in the reaction zone; or alternatively, prior to the ethylenecontacting the catalyst system outside the reaction zone. In anembodiment, wherein ethylene and the organic reaction medium arecontacted, and/or the ethylene is dispersed in the organic reactionmedium prior to ethylene contacting the catalyst system in the reactionzone, the contact and/or dispersion can occur during the reaction zoneperiod of time (e.g., during reaction zone startup), or after thereaction zone period of time (e.g., after reaction zone startup).

In an embodiment, wherein the feedstock mixture comprises ethylene, theC₃₊ olefin, and the organic reaction medium (e.g., at least a portion ofthe organic reaction medium), ethylene, the C₃₊ olefin, and organicreaction medium can be contacted prior to ethylene contacting thecatalyst system. In an embodiment, ethylene and/or the C₃₊ olefin can bedispersed in the organic reaction medium (e.g., at least a portion ofthe organic reaction medium) prior to feedstock mixture contacting thecatalyst system. In some embodiments, ethylene and/or the C₃₊ olefin andthe organic reaction medium can be contacted, and/or the ethylene and/orC₃₊ olefin can be dispersed in the organic reaction medium prior toethylene contacting the catalyst system in the reaction zone; oralternatively, prior to the ethylene contacting the catalyst systemoutside the reaction zone.

In another aspect of the disclosed processes, systems, and/or reactionsystems, the presence of the C₃₊ olefin in the reaction zone for aperiod of time or the introduction/feeding of the C₃₊ olefin to thereaction zone for a period time can be utilized in conjunction with thecontacting ethylene with at least a portion of the organic reactionmedium to form a feedstock mixture prior to contacting ethylene with thecatalyst system. In this aspect, the contacting of the ethylene with theat least a portion of the organic reaction medium can occur during theperiod of time of where the C₃₊ olefin is present in the reaction zonefor a period of time or the where C₃₊ olefin is introduced/fed to thereaction zone; alternatively, after the period of time of where the C₃₊olefin is present in the reaction zone for a period of time or the whereC₃₊ olefin is introduced or fed to the reaction zone; or alternatively,during and after the period of time of where the C₃₊ olefin is presentin the reaction zone for a period of time or the where C₃₊ olefin isintroduced or fed to the reaction zone. In some embodiments, whereethylene is contacted with at least a portion of the organic reactionmedium to form a feedstock mixture prior to contacting ethylene with thecatalyst system, the C₃₊ olefin can be present in the feedstock mixturefor the period of time when the C₃₊ olefin is introduced/fed to thereaction zone. In this situation, the C₃₊ olefin can be contacted 1)with ethylene before the ethylene contacts the organic reaction medium;2) with the organic reaction medium prior to ethylene contacting theorganic reaction medium; and/or 3) with the feedstock mixture after theethylene contacts the organic reaction medium. In an embodiment wherethe C₃₊ olefin is part of the feedstock mixture during the period oftime of where the C₃₊ olefin can be introduced/fed to the reaction zone,the minimum (ethylene +C₃₊ olefin) concentration in the feedstockmixture can be 4 mass %, 10 mass %, 25 mass %, 35 mass %, or 40 mass %based upon the total mass of the feedstock mixture; alternatively oradditionally, the maximum (ethylene +C₃₊ olefin) concentration of thefeedstock mixture cam be 65 mass %, 60 mass %, 55 mass %, 50 mass %, 48mass % based upon the total mass in the feedstock mixture. In anembodiment, the (ethylene +C₃₊ olefin) concentration in the feedstockmixture can from any minimum (ethylene +C₃₊ olefin) concentration in thefeedstock mixture disclosed herein to any maximum (ethylene +C₃₊ olefin)concentration in the feedstock mixture disclosed herein. In somenon-limiting embodiments, the (ethylene +C₃₊ olefin) concentration inthe feedstock mixture can be in a range of from 4 mass % to 60 mass %,from 10 mass % to 60 mass %, from 25 mass % to 55 mass %, 35 mass % to50 mass %, or 40 mass % to 48 mass % based upon the total mass in thefeedstock mixture. Other (ethylene +C₃₊ olefin) concentrations in thefeedstock mixture ranges that can be utilized are readily apparent tothose skilled in the art with the aid of this disclosure.

It is contemplated that the C₃₊ olefin can be present in the reactionzone of the disclosed processes, systems, and reaction systems (e.g.,FIGS. 1 to 3) via: i) combination of the C₃₊ olefin with ethylene beforeethylene is introduced/fed to the reaction zone or before ethylene joinswith organic reaction medium to form the feedstock mixture, ii)combination of the C₃₊ olefin with organic reaction medium before theorganic reaction medium is introduced/fed to the reaction zone or beforeethylene joins with organic reaction medium to form the feedstockmixture, iii) introducing/feeding the C₃₊ olefin directly to thereaction zone; iv) combination of the C₃₊ olefin with the catalystsystem prior to the catalyst system being introduced/fed to the reactionzone or prior to the catalyst system combining with another line outsidethe reaction zone; v) combination of the C₃₊ olefin with the feedstockmixture, vi) combination of the C₃₊ olefin with the dispersed feedstockmixture when the feedstock mixture is dispersed prior to entering thereaction zone; vii) combination of the C₃₊ olefin with a combined feedstream which includes ethylene, the organic reaction medium, and thecatalyst system prior to being introduced/fed to the reaction zone; orviii) any combination of i)-vii). It is also contemplated that when afeedstock mixture comprising ethylene is formed, the feedstock mixturecan be contacted with the catalyst system inside the reaction zone (anexample of which is shown in FIG. 2) or outside the reaction zone (anexample of which is shown in FIG. 3). It is further contemplated thatethylene and the organic reaction medium can be dispersed in thefeedstock mixture prior to introducing the feedstock mixture to thereaction zone and prior to or after contact of the feedstock mixturewith the catalyst system. For example, as shown in FIG. 2, the catalystsystem can be introduced into the reaction zone (via line 152 whichfeeds to the first reaction zone inlet 111, discussed in detail below)separately from feedstock mixture (via line 192 which feeds to thereaction zone inlet 113, also discussed in detail below). Alternatively,as shown in FIG. 3, the catalyst system and the feedstock mixture can becontacted prior to entering the reaction zone 110 (line 152 combineswith dispersed line 192 before the components enter the reaction zoneinlet 119, discussed in detail herein).

In an embodiment, the ethylene oligomer product can be formed (or thereaction zone can have operating conditions) during the reaction zoneperiod of time where the reaction zone C₃₊ olefin:ethylene weight ratiois decreasing. In some embodiments, the ethylene oligomer productformation conditions (or reaction zone operating conditions) can be anydescribed herein with the exception of any ethylene oligomer productformation conditions (or reaction zone operating conditions) which donot take into consideration embodiments and aspects that the reactionzone contains both ethylene and the C₃₊ olefin and/or C₃₊olefin:ethylene reaction zone weight ratio is decreasing (e.g., thereaction zone ethylene concentration, the ethylene to chromium massratio, among others). Alternatively, the ethylene oligomer productformation conditions (or reaction zone operating conditions) can be anyof the ethylene oligomer product formation conditions (or the reactionzone operating conditions) described herein which take intoconsideration that the reaction zone contains both ethylene and the C₃₊olefin and/or C₃₊ olefin:ethylene reaction zone weight ratio isdecreasing (e.g., the reaction zone ethylene concentration, the ethyleneto chromium mass ratio, among others).

Aspects of the disclosure relate to initiating ethylene oligomerization(startup) of a reaction zone in any process, system, and/or reactionsystem (e.g., FIGS. 1 to 3) described herein. Startup can occur when thereaction zone (e.g., reaction zone 110 of FIGS. 1 to 3) is empty orafter reaction zone cleaning (a hard startup) or when the reaction zone(e.g., reaction zone 110 of FIGS. 1 to 3) contains components for anethylene oligomerization reaction but is not producing ethylene oligomerproduct (a soft startup). An example of a soft startup situation can bewhen the flow of ethylene and/or catalyst system is temporarily stoppedto address a process, system or reaction system issue and it is desiredto again start oligomerization reactions without emptying and/orcleaning the reaction zone (e.g., reaction zone 110 of FIGS. 1 to 3).

Startup of any process, system, and/or reaction system (e.g., FIGS. 1 to3) described herein can include a reaction zone commencing stage(hereafter commencing stage), and/or a reaction zone phasing stage(hereafter phasing stage). In some embodiments, the startup of anyprocess, system, and/or reaction system (e.g., FIGS. 1 to 3) describedherein can further include an optional reaction zone filling stage(hereafter filling stage). Temporally, the filling stage can occurbefore the commencing stage and phasing stage.

The filling stage of any process, system, and/or reaction system (e.g.,FIGS. 1 to 3) described herein can involve filling the reaction zone(e.g., reaction zone 110), either empty, already containing componentsfor an ethylene oligomerization reaction, or simultaneously with one ormore components for an ethylene oligomerization reaction, with the C₃₊olefin (e.g., using any one or more appropriate C₃₊ olefin lines inFIGS. 1-3). Reaction zone filling can occur for any period of timeneeded to provide the desired amount of C₃₊ olefin to the reaction zone(or attain any desired reaction zone C₃₊ olefin:ethylene ratio disclosedherein). In an aspect, the reaction zone (e.g., reaction zone 110) canbe filled with the C₃₊ olefin while no ethylene is being fed orintroduced into the reaction zone. Alternatively, the reaction zone(e.g., reaction zone 110) can be filled with the C₃₊ olefin and ethylene(using any C3+ olefin:ethylene weight ratio disclosed herein, or toachieve any reaction zone C₃₊ olefin to ethylene C₃₊ olefin weight ratiodisclosed herein). In some embodiments, the reaction zone can contain,or can be substantially devoid of, organic reaction medium, catalystsystem, hydrogen, and/or scrub agent.

The commencing stage can involve feeding/introducing one or more of theethylene oligomerization components to the reaction zone (e.g., reactionzone 110 of FIGS. 1 to 3). During the commencing stage, the organicreaction medium, the catalyst system, optionally the C₃₊ olefin, andoptionally, hydrogen can be fed/introduced into the reaction zone (e.g.,reaction zone 110 of FIGS. 1 to 3) before ethylene is fed/introduced tothe reaction zone. The organic reaction medium, the catalyst system,optionally the C₃₊ olefin, and optionally hydrogen can be fed/introducedto the reaction zone in any manner and/or any order including adding oneor more simultaneously. For example, a non-limiting order offeeding/introducing the ethylene oligomerization components to thereaction zone during startup can be to first feed/introduce organicreaction medium to the reaction zone (e.g., using any one or moreappropriate lines 162, 191, 192, and 193 in FIGS. 1-3), thenfeed/introduce the catalyst system and optionally hydrogen to thereaction zone in any order (e.g., using the catalyst system feed line152 and/or one or more appropriate lines 144, 142, 191, 102, and 193 forhydrogen flow in FIGS. 1-3), and then feed/introduce the C₃₊ olefin tothe reaction zone (e.g., using any one or more appropriate lines 146 and147 a, b, c, d, e, f, or g in FIGS. 1-3). Another non-limiting order offeeding/introducing the ethylene oligomerization components to thereaction zone during startup can be to first feed/introduce organicreaction medium to the reaction zone (e.g., using any one or moreappropriate lines 162, 191, 192, and 193 in FIGS. 1-3), thenfeed/introduce the C₃₊ olefin to the reaction zone (e.g., using any oneor more appropriate lines 146 and 147 a, b, c, d, e, f, or g in FIGS.1-), and then then feed/introduce the catalyst system and optionallyhydrogen to the reaction zone in any order (e.g., using the catalystsystem feed line 152 and/or one or more appropriate lines 144, 142, 191,102, and 193 for hydrogen flow in FIGS. 1-3). Other orders offeeding/introducing the ethylene oligomerization components to thereaction zone during startup are readily apparent to those havingordinary skill in the art.

In an alternative, the C₃₊ olefin can be fed/introduced to the reactionzone (e.g., reaction zone 110 of FIGS. 1 to 3) in the phasing stage(e.g., introduced simultaneously, but not necessarily combined withethylene). In such alternative, the organic reaction medium, thecatalyst system, and optionally, hydrogen can be fed/introduced to thereaction zone in the commencing stage in any order such as thosedescribed herein. In another alternative, the C₃₊ olefin can befed/introduced to the reaction zone (e.g., reaction zone 110 of FIGS. 1to 3) in the filling stage (e.g., using any one or more appropriate C₃₊olefin feed lines 146 and 147 a, b, c, d, e, f, or g in FIGS. 1-3); thatis, the C₃₊ olefin is not introduced to the reaction zone in thecommencing stage or the phasing stage.

The phasing stage or any process, system, and/or reaction system (e.g.,FIGS. 1 to 3) described herein can involve decreasing the reaction zone(e.g., reaction zone 110 of FIGS. 1 to 3) C₃₊ olefin:ethylene weightratio over a period of time. In an embodiment, decreasing the reactionzone C₃₊ olefin:ethylene weight ratio over a period of time can beaccomplished by feeding/introducing ethylene to a reaction zonecontaining the C₃₊ olefin and/or decreasing the C₃₊ olefin:ethyleneweight ratio of the C₃₊ olefin and ethylene being fed/introduced to thereaction zone. In an aspect, the C₃₊ olefin can be fed/introduced (e.g.,using any one or more appropriate C₃₊ olefin feed lines 146 and 147 a,b, c, d, e, f, or g in FIGS. 1-3) to the reaction zone (e.g., reactionzone 110 of FIGS. 1 to 3) in the filling stage, and then decreasing thereaction zone C₃₊ olefin:ethylene weight ratio by feeding/introducingethylene to the reaction zone using any one or more appropriate lines142, 191, 192, and 193 in FIGS. 1-3. In another aspect, the ethylene andC₃₊ olefin can be fed/introduced (e.g., using any appropriate lines 142,191,192, and 193 for ethylene and one or more appropriate lines 146 and147 a, b, c, d, e, f, or g for C₃₊ olefin) to the reaction zone (e.g.,reaction zone 110 of FIGS. 1-3.) such that C₃₊ olefin:ethylene weightratio fed/introduced to the reaction zone and/or the reaction zone C₃₊olefin:ethylene weight ratio decreases from at least an initial value toless than a final value over a period of time. Embodiments for thedecrease of the reaction zone C₃₊ olefin:ethylene weight ratio and thedecrease of the C₃₊ olefin:ethylene weight ratio fed/introduced to thereaction zone are independently provided herein and can be utilizedwithout limitation to further describe the phasing stage of any process,system, and/or reaction system (e.g., FIGS. 1 to 3) described herein.Without being limited by theory, it is believed that decreasing thereaction zone C₃₊ olefin:ethylene weight ratio during reaction zonestartup can reduce the formation of polymer during reaction zone startup(hard startup or soft startup) as described herein.

In an aspect, the phasing stage can be initiated by feeding/introducingethylene to the reaction (e.g., reaction zone 110 of FIGS. 1-3 using anyappropriate line 142, 191, 192, and 193 for flow of ethylene). Thephasing stage can be initiated after or simultaneously withfeeding/introducing the C₃₊ olefin to the reaction zone (e.g., reactionzone 110 of FIGS. 1-3 using a any appropriate line 142, 191, 192, and193 for flow of ethylene).

The decrease in the reaction zone C₃₊ olefin:ethylene weight ratioand/or the decrease of the C₃₊ olefin:ethylene weight ratiofed/introduced to the reaction zone during the phasing stage is notlimited to a particular technique and can occur via linear decrease(e.g., a constant increase over a given period of time), a step changedecrease (e.g., decrease by changing a set value at set points of timeduring the period of time), or a combination thereof. During the phasingstage the decrease in the reaction zone C₃₊ olefin:ethylene weight ratioand/or the decrease of the C₃₊ olefin:ethylene weight ratiofed/introduced to the reaction zone can be accomplished by increasingthe ethylene flow rate and/or decreasing C₃₊ olefin flowrate to thereaction zone until the desired reaction zone C₃₊ olefin:ethylene weightratio and/or C₃₊ olefin:ethylene weight ratio is achieved.Alternatively, the decrease in the reaction zone C₃₊ olefin:ethyleneweight ratio and/or the decrease of the C₃₊ olefin:ethylene weight ratiofed/introduced to the reaction zone can be accomplished by increasingthe ethylene flow rate and decreasing C₃₊ olefin flowrate to thereaction zone until the desired reaction zone C₃₊ olefin:ethylene weightratio and/or C₃₊ olefin:ethylene weight ratio is achieved.

After ending the phasing stage, ethylene, the organic reaction medium,the catalyst system, and optionally hydrogen can be fed/introduced tothe reaction zone (e.g., reaction zone 110 of FIGS. 1-3) to achieve thedesired ethylene oligomerization operation and/or reaction zoneconditions (e.g., ethylene oligomerization and/or reaction zoneconditions to achieve steady state operation). In an aspect, it iscontemplated that no significant amount of C₃₊ olefin is fed/introducedto the reaction zone during steady state operation of the reaction zone(e.g., reaction zone 110 of FIGS. 1-3). Thus, no significant amount ofC₃₊ olefin is introduced to the reaction zone via a reaction zone inlet(e.g., any reaction zone inlet of FIGS. 1-3) during steady stateoperation. As used herein no significant amount of C₃₊ olefin isfed/introduced to the reaction zone during steady state operation of thereaction zone is defined as a C₃₊ olefin:ethylene weight ratiofed/introduced to the reaction zone of less than 0.1:1, 0.08:1, 0.06:1,0.04:1, 0.02:1, or 0.01:1.

During steady state operation, ethylene, the organic reaction medium,the catalyst system, and optionally, hydrogen can be periodically orcontinuously introduced to the reaction zone (e.g., reaction zone 110 ofFIGS. 1-3). Moreover, in some embodiments, reaction zone effluent can beperiodically or continuously removed from the reaction zone (e.g.,reaction zone 110 of FIGS. 1-3). For example, reaction zone inlets(e.g., the reaction zone inlets of FIGS. 1-3) can be configured toperiodically or continuously introduce the catalyst system, ethylene,organic reaction medium, and optionally hydrogen to the reaction zonewhile a reaction zone outlet (e.g., the reaction zone outlets of FIGS.1-3) can be configured to periodically or continuously discharge orremove the reaction zone effluent from the reaction zone. In someembodiments, the desired ethylene oligomerization operation can includecontacting ethylene with the organic reaction medium to form thefeedstock mixture prior to ethylene contacting the catalyst system.Additionally, when ethylene is contacted with the organic reactionmedium to form the feedstock mixture prior to ethylene contacting thecatalyst system ethylene can be dispersed with the organic reactionmedium prior to ethylene contacting the catalyst system. In anembodiment wherein the ethylene and the organic reaction medium arecontacted, and/or the ethylene can be dispersed in the organic reactionmedium prior to ethylene contacting the catalyst system in the reactionzone (e.g., reaction zone 110 of FIGS. 1-3), the ethylene can contactthe catalyst system in the reaction zone; or alternatively, ethylene cancontact the catalyst system outside the reaction zone.

In an embodiment, any process, system, and/or reaction system describedherein can further comprise preparing the catalyst system. In anembodiment, the catalyst system can be prepared by 1) contacting thechromium component (any described herein) and the aluminoxane compound(any described herein) to form a catalyst system mixture, and 2) agingthe catalyst system mixture in the substantial absence of ethylene toform and aged catalyst system mixture. In an embodiment the catalystsystem mixture can be aged for a period of time. Typically, the minimumaging time can be 5 seconds, 10 seconds, 30 seconds, 1 minute, 5minutes, 10 minutes, or 20 minutes; additionally or alternatively, themaximum aging time can be 48 hours, 36 hours, 24 hours, 18 hours, 12hours, 6 hours, 4 hours, or 2 hours. Generally, the aging time can be ina range from any minimum time disclosed herein to any maximum timedisclosed herein. Accordingly, suitable non-limiting ranges for theaging time can include from 5 seconds to 48 hours, from 10 seconds to 36hours, from 30 seconds to 24 hours, from 1 minute to 18 hours, from 5minutes to 6 hours, from 10 minutes to 4 hours, or from 20 minutes to 2hours. Other appropriate ranges for the aging time are readily apparentfrom this disclosure. In further embodiments, the catalyst systemmixture can be aged at any suitable temperature, ranging fromsub-ambient temperatures, to ambient temperature (approximately 25° C.),to elevated temperatures. While not limited thereto, the catalyst systemmixture can be aged at a temperature in a range from 0° C. to 100° C.,from 10° C. to 75° C., from 15° C. to 60° C., or from 20° C. to 40° C.In these and other embodiments, these temperature ranges also are meantto encompass circumstances where the catalyst system mixture can be agedat a series of different temperatures, instead of at a single fixedtemperature, falling within the respective ranges. In a non-limitingembodiment, a substantial absence of ethylene can be a maximum molarratio of ethylene to chromium component of 5:1, 4:1, 3:1, 2:1, 1:1,0.5:1, 0.25:1, or 0.1:1. In some non-limiting embodiments, thesubstantial absence of ethylene can be a maximum ethylene partialpressure 10 psig (69 kPa), 5 psig (34 kPa), 4 psig (28 kPa), 3 psig (21kPa), 2 psig (14 kPa), 1 psig (7 kPa), or 0.5 psig (3.4 kPa). In someembodiments, the catalyst system can be formed by contacting a diluentand/or a solvent with the chromium component (any described herein) andthe aluminoxane (any described herein). In an embodiment, the diluentand/or solvent can be any organic reaction medium described herein. Inembodiments where the catalyst system can be formed by contacting adiluent and/or a solvent with the chromium component (any describedherein) and the aluminoxane, the chromium component to solvent and/ordiluent weight ratio can range from 1:100 to 1:15,000, or 1:150 to1:10,000.

While in one embodiment the catalyst system can be prepared prior toentering the reaction zone, the processes, system, and reaction systemsdescribed herein, the catalyst system also can be formed in-situ withinthe reaction zone. That is to say that all of the components of thecatalyst system (e.g., the chromium component comprising a chromiumcompound, the heteroatomic ligand, and the aluminoxane; oralternatively, the chromium component comprising a heteroatomic ligandchromium compound complex, and the aluminoxane) do not contact eachother until after they are introduced/fed into the reaction zone. In thein-situ catalyst system preparation embodiments of the processes,system, and reaction systems described herein, two or more components ofthe catalyst system can be separately introduced/fed to reaction zone(e.g., via two or more feed lines and reaction zone inlets). Generally,the two or more separately introduced/fed catalyst system components canbe i) introduced/fed to the reaction zone separately from the otherfeeds to the reaction zone, ii) introduced/fed with other feeds to thereaction zone, or iii) some introduced/fed to the reaction zone separatefrom the other feeds to the reaction zone and some introduced/fed withother feeds to the reaction zone. For example, for a catalyst systemcomprising i) a chromium component comprising a chromium compound, ii) aheteroatomic ligand, and iii) an aluminoxane, the chromium componentcomprising the chromium compound and heteroatomic ligand can beintroduced/fed to the reaction zone separately (either individually orin combination) from the other feeds to the reaction zone while thealuminoxane can be introduced/fed to the reaction zone with the organicreaction medium or introduced/fed separately from the feeds to thereaction zone; or alternatively, the chromium component comprising thechromium compound and the heteroatomic ligand can be introduced/fed tothe reaction zone with a portion of the organic reaction medium (eitherseparately or in combination) while the aluminoxane can beintroduced/fed to the reaction zone with a different portion of theorganic reaction medium or introduced/fed separately from the otherfeeds to the reaction zone. In another example, for a catalyst systemcomprising i) a chromium component comprising a heteroatomic ligandchromium compound complex, and ii) an aluminoxane, the chromiumcomponent comprising the heteroatomic ligand chromium compound complexcan be introduced/fed to the reaction zone separately from the otherfeeds to the reaction zone while the aluminoxane can be introduced/fedto the reaction zone with the organic reaction medium or introduced/fedseparately from the feeds to the reaction zone; or alternatively, thechromium component comprising the heteroatomic ligand chromium compoundcomplex can be introduced/fed to the reaction zone with a portion of theorganic reaction medium while the aluminoxane can be introduced/fed tothe reaction zone with a different portion of the organic reactionmedium or introduced/fed separately from the other feeds to the reactionzone. These herein provided examples are non-limiting and are only meantto describe possible ways the catalyst system components can beseparately introduced/fed to the reaction zone for the in-situ formationof the catalyst system within the reaction zone. Other ways ofseparately introducing/feeding two or more components of the catalystsystem to the reaction zone are readily apparent to those havingordinary skill in the art.

FIG. 1 shows a process flow diagram of a reaction system 100 accordingto the present disclosure. The system 100 includes one or more of anethylene source 140 in fluid communication with an ethylene feed line142; a C₃₊ olefin source 145 in communication with a C₃₊ feed line 146;a catalyst system source 150 in fluid communication with a catalystsystem feed line 152; an organic reaction medium source 160 in fluidcommunication with an organic reaction medium feed line 162; an optionalscrub agent source 170 in communication with a scrub agent feed line172; an optional hydrogen feed line 144 feeding to the ethylene feedline 142; an optional pump 180; a reaction zone 110 having a firstreaction zone inlet 111, a second reaction zone inlet 213, a thirdreaction zone inlet 215, a fourth reaction zone inlet 115, and areaction zone outlet 117 representing one or more reaction zone outlets;and a heat exchanger 120. It is contemplated that the reaction system100 of FIG. 1 can include appropriate equipment (e.g., valves, controldevices, sensors, electrical writing, insulation) which are not shown inFIG. 1 yet can be included according to those skilled in the art withthe aid of this disclosure.

The first reaction zone inlet 111 (representing one or more reactionzone inlets) can be configured to introduce a catalyst system (which canbe optionally combined with C₃₊ olefin for a period of time) asdescribed herein to the reaction zone 110, the second reaction zoneinlet 213 (representing one or more reaction zone inlets) can beconfigured to introduce ethylene (which can be optionally combined withC₃₊ olefin for a period of time) to the reaction zone 110, the thirdreaction zone inlet 215 (representing one or more reaction zone inlets)can be configured to introduce organic reaction medium (which can beoptionally combined with C₃₊ olefin for a period of time) to thereaction zone 110, and the reaction zone outlet 117 (representing one ormore reaction zone outlets) can be configured to discharge or remove areaction zone effluent comprising an ethylene oligomer product from thereaction zone 110 via line 118. Valve 130 can be used in line 118 tocontrol a flow of the reaction zone effluent in line 118 and/or tocontrol a pressure of the reaction zone 110. Reaction zone effluent inline 118 can then feed to equipment (not shown) for isolating variousstreams (e.g., the desired oligomer) from the reaction zone effluent.

The catalyst system can flow through catalyst system feed line 152 fromthe catalyst system source 150 to the first reaction zone inlet 111,where the catalyst system can be fed to the reaction zone 110. AlthoughFIG. 1 is described as flowing a pre-mixed or pre-prepared catalystsystem to the reaction zone 110 via line 152, an alternative aspect ofthe disclosed catalyst systems can be one where two or more of thecomponents of the catalyst system can be separately introduced/fed tothe reaction zone where the catalyst system in prepared in-situ withinreaction zone 110 (as opposed to ex-situ mixing or preparation outsidethe reaction zone 110). That is, in an aspect of the disclosed reactionsystem, the catalyst system components can be introduced/fed separatelyto the reaction zone 110. For example, for a catalyst system comprisingi) a chromium component comprising a chromium compound, ii) aheteroatomic ligand, and iii) an aluminoxane, the chromium component andheteroatomic ligand can flow to the reaction zone 110 via line 152,while the aluminoxane can flow to the reaction zone 110 via one or moreof: line 142; line 162; line 172; lines 146, 147 a, and 142; lines 146,147 b, and 162; lines 146 and 147 c; and directly to the reaction zone110 via another line and one of the reaction zone inlets 215, 215, and115 or another reaction zone inlet (not shown). For a catalyst systemcomprising i) a chromium component comprising a heteroatomic ligandchromium compound complex, and ii) an aluminoxane, the chromiumcomponent can flow to the reaction zone 110 via line 152, while thealuminoxane can flow to the reaction zone 110 via one or more of: line142; line 162; line 172; lines 146, 147 a, and 142; lines 146, 147 b,and 162; lines 146 and 147 c; and directly to the reaction zone 110 viaanother line and one of the reaction zone inlets 215, 215, and 115 oranother reaction zone inlet. The herein described examples arenon-limiting and are only meant to describe possible ways the catalystsystem components can be separately introduced/fed to the reaction zone110 for the in-situ formation of the catalyst system within the reactionzone. Any description of line 152 in FIG. 1 as containing the catalystsystem herein can equally apply to aspects where only a part of thecatalyst system is in line 152 while other parts are fed to the reactionzone 110 elsewhere in the system 100 and/or processes implementedtherein.

The catalyst system feed line 152 can optionally include a solventand/or diluent with the catalyst system. The solvent and/or diluent canbe any organic reaction medium described herein. In an embodiments, thesolvent and/or diluent can be the organic reaction medium utilized inthe process, system, or reaction system. The catalyst system can bedispersed in the solvent and/or diluent in the catalyst system feed line152. For example, the catalyst system feed line 152 can include a mixingdevice (not shown), similar to mixing device 190 (described herein)discussed for FIG. 2 or in a precontactor apparatus (not shown), whichcan be configured to disperse the catalyst system in the diluent priorto the catalyst system entering the reaction zone 110 via first reactionzone inlet 111. When solvent and/or diluent and the catalyst system arepresent in the catalyst system feed line 152 of FIG. 1, thechromium:solvent and/or diluent mass ratio can be any disclosed herein.

Optionally, scrub agent (described herein) can flow in the scrub agentfeed line 172. In an embodiment some or all of the aluminoxane of thecatalyst system can flow in the scrub agent feed line 172. For example,all of the aluminoxane of the catalyst system can flow in scrub agentfeed line 172 in the in-situ generation of the catalyst system; oralternatively, the aluminoxane can flow in both the catalyst system feedline 152 and the scrub agent feed line 172. In an embodiment, the scrubagent may not be an aluminoxane of the catalyst system.

Organic reaction medium can flow in organic reaction medium feed line162 from the organic reaction medium source 160 to the suction side 181of pump 180.

At least a portion of the organic reaction medium can be contacted witha scrub agent (e.g., an alkylaluminum compound, any described herein)prior to introduction to the reaction zone 110. FIG. 1 shows scrub agentcan be added via feed line 172 to the organic reaction medium feed line162 such that line 162 can contain both the scrub agent and the organicreaction medium. Alternatively, the scrub agent may not be combined withthe organic reaction medium in the organic reaction medium feed line162. In a non-limiting embodiment where the catalyst system is formedin-situ within reaction zone 110, an aluminoxane can be utilized as thescrub agent and can be all or a portion of the aluminoxane component ofthe catalyst system. Alternatively, the scrub agent is not combined withthe organic reaction medium in the organic reaction medium. The scrubagent is independently disclosed herein and can be utilized to furtherdescribed reaction system 100. The scrub agent is independentlydisclosed herein and can be utilized to further described reactionsystem 100.

In embodiments where the organic reaction medium and ethylene arecontacted to form a feedstock mixture, at least a portion of the organicreaction medium can be contacted with the scrub agent (e.g., analkylaluminum compound, any described herein) prior to contact of theportion of organic reaction medium with ethylene. FIG. 1 shows the scrubagent can be added via line 172 to the organic reaction medium feed line162, before the organic reaction medium contacts ethylene viacombination of the organic reaction medium feed line 162 with theethylene feed line 142. The scrub agent is independently disclosedherein and can be utilized to further describe reaction system 100.

In FIG. 1, all of the organic reaction medium can be fed to the reactionzone via line 162. However, as is discussed herein, it is contemplatedthat only a portion of the total amount of organic reaction medium whichis used in the system 100 is in line 162 and optionally contacted withthe scrub agent prior to introduction to the reaction zone 110; e.g.,the other portions can be mixed with the catalyst system in catalystsystem feed line 152.

Ethylene flows in ethylene feed line 142 from the ethylene source 140 tothe second reaction zone inlet 213.

Hydrogen optionally can be used to control the selective ethyleneoligomerization reaction. The hydrogen can be fed into the ethylene feedline 142 via hydrogen feed line 144. The combination of hydrogen withethylene in the ethylene feed line 144 can be upstream of valve 143 asshown in FIG. 1; or alternatively, downstream of valve 143. While thehydrogen feed line 144 in FIG. 1 is shown as feeding to the ethylenefeed line 142, it is contemplated that the hydrogen feed line 144 canfluidly connect to any reaction zone inlet (e.g., reaction zone inlet111, reaction zone inlet 115, reaction zone inlet 213, or reaction zoneinlet 215) directly or via another line (e.g., line 146, line 147 a, b,c, or d, line 152, line 162, or line 172).

The C₃₊ olefin can be introduced, for a period of time, to reactionsystem 100 via one or more of lines 147 a-d (the alternative naturebeing shown as dashed lines). For example, the C₃₊ olefin, which can beintroduced for a period of time, can flow from the C₃₊ olefin source 145via line 146 and one or more of: i) line 147 a to combine with ethyleneflowing in ethylene feed line 142, ii) line 147 b to combine with theorganic reaction medium flowing in line 162, iii) 147 c to add the C₃₊olefin directly to the reaction zone 110, and iv) line 147 d to combinewith the catalyst system flowing in line 152.

When introducing the C₃₊ olefin, which can be introduced for a period oftime, via line 146 and line 147 a, the C₃₊ olefin can combine withethylene flowing in ethylene feed line 142. The ethylene feed line 142(comprising ethylene, the C₃₊ olefin, and optionally hydrogen) canconnect to the reaction zone 110 via the second reaction zone inlet 213.In the aspect where the C₃₊ olefin is introduced which can be introducedfor a period of time via line 146 and line 147 a, the C₃₊ olefin canflow via lines 146, 147 a, and 142.

When introducing the C₃₊ olefin for a period of time via line 146 andline 147 b, the C₃₊ olefin can combine with the organic reaction medium(which can optionally previously combined with the scrub agent) flowingin the organic reaction medium feed line 162. The organic reactionmedium line 162 (comprising the organic reaction medium, the C₃₊ olefin,and optionally scrub agent) can flow to the reaction zone 110 via thethird reaction zone inlet 215. In the aspect where the C₃₊ olefin isintroduced for a period of time via line 146 and line 147 b, the C₃₊olefin can flow via lines 146, 147 b, and 162 to the reaction zone 110.

When introducing the C₃₊ olefin for a period of time via line 146 andline 147 c, the C₃₊ olefin can flow directly to the reaction zone 110via the fourth reaction zone inlet 115 which can be configured tointroduce the C₃₊ olefin for a period of time to the reaction zone 110.

When introducing the C₃₊ olefin for a period of time via line 146 andline 147 d, the C₃₊ olefin can combine with the catalyst system flowingin catalyst system feed line 152. In such an aspect, the catalyst systemcan flow for a period of time with the C₃₊ olefin in line 152 to thereaction zone 110 via the first reaction zone inlet 111. With respect tothe timing of the flow of the C₃₊ olefin relative to the flow ofethylene for a period of time, the flow of C₃₊ olefin can commencebefore or simultaneously with the flow of ethylene regardless which oflines 147 a, 147 b, 147 c, and/or 147 d the C3+ olefin flows.Alternatively, the flow of the C₃₊ olefin can commence before the flowof ethylene (when the reaction zone 110 is empty, for example, duringhard startup, or when the reaction zone 110 already contains material,for example, in a soft startup after temporary cessation of the flow ofethylene and/or catalyst system to the reaction zone 110 to addressprocess or system issues), then be stopped temporarily, and then againcommenced before or at the same time (simultaneously) as the flow ofethylene and/or catalyst system. With respect to the timing of the flowof the C₃₊ olefin relative to the flow of catalyst system for a periodof time, the flow of the C₃₊ olefin can commence before, simultaneously,or after the flow of the catalyst system regardless of which lines 147a, 147 b, 147 c, and/or 147 d the C₃₊ olefin flows. With respect to thetiming of the flow of the C₃₊ olefin relative to the flow of organicreaction medium for a period of time, the flow of the C₃₊ olefin cancommence before, simultaneously, or after the flow of the organicreaction medium regardless of which lines 147 a, 147 b, 147 c, and/or147 d the C₃₊ olefin flows. With respect to the timing of the flow ofthe C₃₊ olefin relative to the flow of scrub agent for a period of time,the flow of the C₃₊ olefin can commence before, simultaneously, or afterthe flow of the scrub agent regardless of which lines 147 a, 147 b, 147c, and/or 147 d the C₃₊ olefin flows.

It is noted that in the system 100 of FIG. 1, ethylene can be fed to thereaction zone 110 separately with respect to the catalyst system andwith respect to the organic reaction medium. That is, ethylene can befed to the reaction zone 110 via line 142 and via second reaction zoneinlet 213; while, the catalyst system can be fed to the reaction zone110 via line 152 and via first reaction zone inlet 111, and while theorganic reaction medium can be fed to the reaction zone 110 via line 162and via the third reaction zone inlet 215.

The separately fed ethylene can be substantially free of the catalystsystem or at least a chromium component of the catalyst system. By“substantially free” it is meant that the ethylene has equal to or lessthan 1.0, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 wt. % of thecatalyst system present based on the total weight of the catalyst systementering the reaction zone 110.

FIG. 2 shows a process flow diagram of a reaction system 200 accordingto the present disclosure. The system 200 includes one or more of anethylene source 140 in fluid communication with an ethylene feed line142; a C₃₊ olefin source 145 in communication with a C₃₊ feed line 146;a catalyst system source 150 in fluid communication with a catalystsystem feed line 152; an organic reaction medium source 160 in fluidcommunication with an organic reaction medium feed line 162; an optionalscrub agent source 170 in communication with a scrub agent feed line172; an optional hydrogen feed line 144 feeding to the ethylene feedline 142; an optional pump 180; an optional mixing device 190; areaction zone 110 having a first reaction zone inlet 111, a secondreaction zone inlet 113, an optional third reaction zone inlet 115, anda reaction zone outlet 117 representing one or more reaction zoneoutlets; and a heat exchanger 120. It is contemplated that the reactionsystem 200 of FIG. 2 can include appropriate equipment (e.g., valves,control devices, sensors, electrical writing, insulation) which are notshown in FIG. 2 yet can be included according to those skilled in theart with the aid of this disclosure.

The first reaction zone inlet 111 (representing one or more reactionzone inlets) can be configured to introduce a catalyst system (which canbe optionally combined with C₃₊ olefin for a period of time) asdescribed herein to the reaction zone 110, the second reaction zoneinlet 113 (representing one or more reaction zone inlets) can beconfigured to introduce a feedstock mixture (which can be optionallycombined with C₃₊ olefin for a period of time) to the reaction zone 110,and the reaction zone outlet 117 (representing one or more reaction zoneoutlets) can be configured to discharge or remove a reaction zoneeffluent comprising an ethylene oligomer product from the reaction zone110 via line 118. Valve 130 can be used in line 118 to control a flow ofthe reaction zone effluent in line 118 and/or to control a pressure ofthe reaction zone 110. Reaction zone effluent in line 118 can then feedto equipment (not shown) for isolating various streams (e.g., thedesired oligomer) from the reaction zone effluent.

The catalyst system can flow through catalyst system feed line 152 fromthe catalyst system source 150 to the first reaction zone inlet 111,where the catalyst system can be fed to the reaction zone 110. AlthoughFIG. 2 is described as flowing a pre-mixed or pre-prepared catalystsystem to the reaction zone 110 via line 152, an alternative aspect ofthe disclosed catalyst systems can be one where two or more of thecomponents of the catalyst system can be separately introduced/fed tothe reaction zone where the catalyst system in prepared in-situ withinof the reaction zone 110 (as opposed to ex-situ mixing or preparationoutside the reaction zone 110). That is, in an aspect of the disclosedreaction system, the catalyst system components can be introduced/fedseparately to the reaction zone 110. For example, for a catalyst systemcomprising i) a chromium component comprising a chromium compound, ii) aheteroatomic ligand, and iii) an aluminoxane, the chromium component andheteroatomic ligand can flow to the reaction zone 110 via line 152,while the aluminoxane can flow to the reaction zone 110 via one or moreof: lines 172, 162, 191, and 192; lines 162, 191, and 192; lines 142,191, and 192; lines 191 and 192; line 192; and directly to the reactionzone 110 via another line and/or another reaction zone inlet (notshown). For a catalyst system comprising i) a chromium componentcomprising a heteroatomic ligand chromium compound complex, and ii) analuminoxane, the chromium component can flow to the reaction zone 110via line 152, while the aluminoxane can flow to the reaction zone 110via one or more of: lines 172, 162, 191, and 192; lines 162, 191, and192; lines 142, 191, and 192; lines 191 and 192; line 192; and directlyto the reaction zone 110 via another line and/or another reaction zoneinlet. The herein described examples are non-limiting and are only meantto describe possible ways the catalyst system components can beseparately introduced/fed to the reaction zone 110 for the in-situformation of the catalyst system with the reaction zone. Any descriptionof line 152 in FIG. 2 as containing the catalyst system herein canequally apply to aspects where only a part of the catalyst system is inline 152 while other parts are fed to the reaction zone 110 elsewhere inthe system 200 and/or processes implemented therein.

The catalyst system feed line 152 can optionally include a solventand/or diluent with the catalyst system. The solvent and/or diluent canbe any organic reaction medium described herein. In some embodiments,the solvent and/or diluent can be the organic reaction medium used inthe feedstock mixture. The catalyst system can be dispersed in thesolvent and/or diluent in the catalyst system feed line 152. Forexample, the catalyst system feed line 152 can include a mixing device,similar to mixing device 190 (described herein) or in a precontactorapparatus (not shown), which can be configured to disperse the catalystsystem in the diluent prior to the catalyst system entering the reactionzone 110 via first reaction zone inlet 111. When solvent and/or diluentand the catalyst system are present in the catalyst system feed line 152of FIG. 2, the chromium:solvent and/or diluent mass ratio can be anydisclosed herein.

Optionally, scrub agent (described herein) can flow in the scrub agentfeed line 172. In an embodiment some or all of the aluminoxane of thecatalyst system can flow in the scrub agent feed line 172. For example,all of the aluminoxane of the catalyst system can flow in scrub agentfeed line 172 in the in-situ generation of the catalyst system; oralternatively, the aluminoxane can flow in both the catalyst system feedline 152 and the scrub agent feed line 172. In an embodiment, the scrubagent may not be an aluminoxane of the catalyst system.

In embodiments where the organic reaction medium and ethylene arecontacted to form a feedstock mixture, at least a portion of the organicreaction medium can be contacted with the scrub agent (e.g., analkylaluminum compound, any described herein) prior to contact of theportion of organic reaction medium with ethylene. FIG. 2 shows the scrubagent can be added via line 172 to the organic reaction medium feed line162, before the organic reaction medium contacts ethylene viacombination of the organic reaction medium feed line 162 with theethylene feed line 142. The scrub agent is independently disclosedherein and can be utilized to further describe reaction system 200.

Organic reaction medium (optionally combined with the catalyst system)can flow in organic reaction medium feed line 162 from the organicreaction medium source 160, through the pump 180, and to the point wherethe ethylene feed line 142 and the organic reaction medium feed line 162join.

At least a portion of the organic reaction medium can be contacted witha scrub agent (e.g., an alkylaluminum compound, any described herein)prior to introduction to the reaction zone 110. FIG. 2 shows scrub agentcan be added via feed line 172 to the organic reaction medium feed line162 such that line 162 can contain both the scrub agent and the organicreaction medium. Alternatively, the scrub agent may not be combined withthe organic reaction medium in the organic reaction medium feed line162. In a non-limiting embodiment where the catalyst system is formedin-situ within reaction zone 110, an aluminoxane can be utilized as thescrub agent and all or a portion of the aluminoxane component of thecatalyst system. The scrub agent is independently disclosed herein andcan be utilized to further described reaction system 200.

In embodiments where the organic reaction medium and ethylene arecontacted to form a feedstock mixture, at least a portion of the organicreaction medium can be contacted with the scrub agent (e.g., analkylaluminum compound) prior to contact of the portion of organicreaction medium with ethylene. FIG. 2 shows the scrub agent can be addedvia line 172 to the organic reaction medium feed line 162, before theorganic reaction medium contacts ethylene via combination of the organicreaction medium feed line 162 with the ethylene feed line 142.Alternatively, the scrub agent may not be combined with the organicreaction medium in the organic reaction medium feed line 162. The scrubagent is independently disclosed herein and can be utilized to furtherdescribed reaction system 200.

In FIG. 2, all of the organic reaction medium can be fed to the reactionzone via line 162 However, as is discussed herein, it is contemplatedthat only a portion of the total amount of organic reaction medium whichis used in the system 200 can be in line 162 and optionally contactedwith the scrub agent prior to introduction to the reaction zone 110;e.g., the other portions can be mixed with the catalyst system incatalyst system feed line 152 and/or can be included in a bypass linewhich feeds directly to the reaction zone 110. Alternatively, the scrubagent may not be combined with the organic reaction medium, and theorganic reaction medium feed line 162 can flow directly to the suctionside 181 of pump 180.

Ethylene (which can be optionally combined with C₃₊ olefin for a periodof time and/or optionally combined with hydrogen) can flow in ethylenefeed line 142 from the ethylene source 140 and can combine with organicreaction medium (which can be optionally previously combined with scrubagent and/or C₃₊ olefin) flowing in line 162 on the head side 182 of thepump 180. Alternatively, ethylene can be combined with the organicreaction medium flowing in line 162 on the suction side 181 of the pump180.

Combination of the ethylene in line 142 with the organic reaction mediumin line 162 can yield a feedstock mixture in feedstock mixture feed line191. The feedstock mixture can flow through an optional mixing device190 where ethylene and the organic reaction medium (which can beoptionally previously combined with scrub agent and/or C₃₊ olefin) canbe dispersed, and subsequently can flow via dispersed feedstock mixturefeed line 192 as a dispersed feedstock mixture to the second reactionzone inlet 113.

Hydrogen optionally can be used to control oligomerization reactions.The optional hydrogen can be fed into the ethylene feed line 142 ofreaction system 200 via hydrogen feed line 144. The combination ofhydrogen with ethylene in the ethylene feed line 144 can be upstream ofvalve 143 as shown in FIG. 2; or alternatively, downstream of valve 143.While the hydrogen feed line 144 in FIG. 2 is shown as feeding to theethylene feed line 142, it is contemplated that the hydrogen feed line144 can fluidly connect to any reaction zone inlet (e.g., reaction zoneinlet 111, reaction zone inlet 113, or reaction zone inlet 115) directlyor via another line (e.g., line 146, line 147 a, b, c, d, e, or f, line152, line 162, line 172, line 191, or line 192).

The C₃₊ olefin can be introduced, for a period of time, to reactionsystem 200 via any one or more of lines 147 a-f (the alternative naturebeing shown as dashed lines). For example, the C₃₊ olefin, which can beintroduced/fed for a period of time to the reaction zone, can flow fromthe C₃₊ olefin source 145 via line 146 and: i) via line 147 a to combinewith ethylene flowing in ethylene feed line 142, before ethylene joinswith organic reaction medium flowing in feed line 162 to form thefeedstock mixture in feedstock mixture line 191, ii) via line 147 b tocombine with the organic reaction medium flowing in line 162, before theorganic reaction medium joins with ethylene to form the feedstockmixture in line 191, iii) via line 147 c to add the C₃₊ olefin directlyto the reaction zone 110, iv) via line 147 d to combine with thecatalyst system flowing in line 152; v) via line 147 e to combine withthe feedstock mixture flowing in line 191, vi) via 147 f to combine withthe dispersed feedstock mixture flowing in line 192, or vii) anycombination of i)-vi).

When introducing the C₃₊ olefin for a period of time via line 146 andline 147 a, the C₃₊ olefin can combine with ethylene flowing in ethylenefeed line 142. The ethylene feed line 142 (comprising ethylene, the C₃₊olefin, and optionally hydrogen) can join with the organic reactionmedium (which can be optionally previously combined with scrub agent)line 162 to form the feedstock mixture line 191. That is, in an aspectwhere the C₃₊ olefin flows in line 147 a, the feedstock mixture includesethylene, organic reaction medium (which can be optionally previouslycombined with scrub agent), and the C₃₊ olefin (and optionallyhydrogen). The feedstock mixture can flow into the optional mixingdevice 190 where ethylene, the organic reaction medium (which can beoptionally previously combined with scrub agent), the C₃₊ olefin, andoptionally hydrogen are dispersed in the feedstock mixture. Thedispersed components in line 191 can flow from the optional mixingdevice 190 in the dispersed feedstock mixture line 192 to the reactionzone 110 via the second reaction zone inlet 113. In the aspect where theC₃₊ olefin is introduced via line 146 and line 147 a, the C₃₊ olefin canflow via lines 146, 147 a, 142, 191, and 192 to the reaction zone 110.

When introducing the C₃₊ olefin for a period of time via line 146 andline 147 b, the C₃₊ olefin can combine with the organic reaction medium(which can be optionally previously combined with scrub agent) flowingin the organic reaction medium feed line 162. The organic reactionmedium line 162 (comprising the organic reaction medium, the C₃₊ olefin,and optionally scrub agent) can join with the ethylene feed line 142(comprising ethylene and optionally hydrogen) to form the feedstockmixture line 191. That is, in an aspect where the C₃₊ olefin flows inline 147 b, the feedstock mixture in line 191 includes ethylene, organicreaction medium, and the C₃₊ olefin (and optionally scrub agent and/orhydrogen). The feedstock mixture can flow into the optional mixingdevice 190 where ethylene, the organic reaction medium, and the C₃₊olefin (and optionally the scrub agent and/or hydrogen) can be dispersedin the feedstock mixture. The dispersed feedstock mixture can flow fromthe optional mixing device 190 in the dispersed feedstock mixture line192 to the reaction zone 110 via the second reaction zone inlet 113. Inthe aspect where the C₃₊ olefin is introduced via line 146 and line 147b, the C₃₊ olefin can flow via lines 146, 147 b, 162, 191, and 192 tothe reaction zone 110.

When introducing the C₃₊ olefin for a period of time via line 146 andline 147 c, the C₃₊ olefin flows directly to the reaction zone 110 viathe reaction zone inlet 115 which is configured to introduce the C₃₊olefin to the reaction zone 110.

When introducing the C₃₊ olefin for a period of time via line 146 andline 147 d, the C₃₊ olefin can combine with the catalyst system flowingin catalyst system feed line 152. In such an aspect, the catalyst systemcan flow for a period of time with the C₃₊ olefin in line 152 to thereaction zone 110 via the first reaction zone inlet 111. In the aspectwhere the C₃₊ olefin is introduced via line 146 and line 147 d, the C₃₊olefin can flow via lines 146, 147 d, and 152 to the reaction zone 110via the first reaction zone inlet 111.

When introducing the C₃₊ olefin for a period of time via line 146 andline 147 e, the C₃₊ olefin can combine with the feedstock mixture inline 191. In such an aspect, the feedstock mixture entering the optionalmixing device 190 can contain the C₃₊ olefin in addition to ethylene,and the organic reaction medium (and optionally the scrub agent and/orhydrogen). In the mixing device 190, ethylene, the organic reactionmedium, and the C₃₊ olefin (and optionally the scrub agent and/orhydrogen) can be dispersed in the feedstock mixture. The dispersedfeedstock mixture flows from the optional mixing device 190 in dispersedfeedstock mixture line 192 to the reaction zone 110 via the secondreaction zone inlet 113. In the aspect where the C₃₊ olefin isintroduced via line 146 and line 147 e, the C₃₊ olefin can flow for aperiod of time via lines 146, 147 e, 191, and 192 to the reaction zone110.

When introducing the C₃₊ olefin for a period of time via line 146 andline 147 f, the C₃₊ olefin can combine with the dispersed feedstockmixture in line 192. In such an aspect, the feedstock mixture enteringthe mixing device 190 can comprise ethylene and organic reaction medium(and optionally scrub agent and/or hydrogen); the dispersed feedstockmixture exiting the optional mixing device 190 can comprise ethylene andthe organic reaction medium (optionally scrub agent and/or hydrogen)dispersed in the feedstock mixture; and after line 147 c containing theC₃₊ olefin can combine with line 192, the dispersed feedstock mixtureadditionally can comprise the C₃₊ olefin. In certain aspects, the C₃₊olefin may or may not be dispersed in the dispersed feedstock mixturecontained in line 192. The dispersed feedstock mixture additionallycontaining the C₃₊ olefin can flow to the reaction zone 110 via thesecond reaction zone inlet 113. In the aspect where the C₃₊ olefin isintroduced via line 146 and line 147 f, the C₃₊ olefin can flow vialines 146, 147 f, and 192 to the reaction zone 110.

With respect to the timing of the flow of the C₃₊ olefin relative to theflow of ethylene for a period of time, the flow of C₃₊ olefin cancommence before or simultaneously with the flow of ethylene regardlesswhich of lines 147 a, 147 b, 147 c, 147 d, 147 e, and/or 147 f the C₃₊olefin flows. Alternatively, the flow of the C₃₊ olefin can commencebefore the flow of ethylene (when the reaction zone 110 is empty, forexample, during hard startup, or when the reaction zone 110 alreadycontains material, for example, in a soft startup after temporarycessation of the flow of ethylene and/or catalyst system to the reactionzone 110 to address process or system issues), then be stoppedtemporarily, and then again commenced before or at the same time(simultaneously) as the flow of ethylene and/or catalyst system. Withrespect to the timing of the flow of the C₃₊ olefin relative to the flowof catalyst system for a period of time, the flow of the C₃₊ olefin cancommence before, simultaneously, or after the flow of the catalystsystem regardless of which lines 147 a, 147 b, 147 c, 147 d, 147 e,and/or 147 f the C₃₊ olefin flows. With respect to the timing of theflow of the C₃₊ olefin relative to the flow of organic reaction mediumfor a period of time, the flow of the C₃₊ olefin can commence before,simultaneously, or after the flow of the organic reaction mediumregardless of which lines 147 a, 147 b, 147 c, 147 d, 147 e, and/or 147f the C₃₊ olefin flows. With respect to the timing of the flow of theC₃₊ olefin relative to the flow of scrub agent for the period of time,the flow of the C₃₊ olefin can commence before, simultaneously, or afterthe flow of the scrub agent regardless of which lines 147 a, 147 b, 147c, 147 d, 147 e, and/or 147 f the C₃₊ olefin flows.

It is noted that in the system 200 of FIG. 2, the feedstock mixturecomprising ethylene and at least a portion of the organic reactionmedium (in the case of FIG. 2, all of the organic reaction medium usedin system 200) can be fed to the reaction zone 110 separately withrespect to the catalyst system. That is, the feedstock mixture is fed tothe reaction zone 110 via lines 191 and 192 and via second reaction zoneinlet 113; while, the catalyst system can be fed to the reaction zone110 via line 152 and via first reaction zone inlet 111.

The separately fed feedstock mixture in any of lines 191 and 192 issubstantially free of the catalyst system or at least a chromiumcomponent of the catalyst system. By “substantially free” it is meantthat the feedstock mixture has equal to or less than 1.0, 0.9, 0.8, 0.7,0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 wt. % of the catalyst system presentbased on weight of the feedstock mixture entering the reaction zone 110.

FIG. 3 shows a process flow diagram of another reaction system 300according to the present disclosure. The system 300 includes one or moreof an ethylene source 140 in fluid communication with an ethylene feedline 142; a catalyst system source 150 in fluid communication with acatalyst system feed line 152; a C₃₊ olefin source 145 in communicationwith a C₃₊ feed line 146; an organic reaction medium source 160 in fluidcommunication with an organic reaction medium feed line 162; an optionalscrub agent source 170 in communication with a scrub agent feed line172; an optional hydrogen feed line 144 feeding to the ethylene feedline 142; an optional pump 180; an optional mixing device 190; areaction zone 110 having a reaction zone inlet 119, an optional reactionzone inlet 115 for C₃₊ olefin, and a reaction zone outlet 117representing one or more reaction zone outlets; and a heat exchanger120. It is contemplated that the reaction system 300 of FIG. 3 caninclude appropriate equipment (e.g., valves, control devices, sensors,electrical writing, insulation) which are not shown in FIG. 3 yet wouldbe included according to those skilled in the art with the aid of thisdisclosure.

The reaction zone inlet 119 (representing one or more reaction zoneinlets) can be configured to introduce the catalyst system and thefeedstock mixture to the reaction zone 110, and the reaction zone outlet117 (representing one or more reaction zone outlets) can be configuredto discharge a reaction zone effluent comprising an ethylene oligomerproduct from the reaction zone 110 via line 118. Valve 130 can be usedin line 118 to control a flow of the reaction zone effluent in line 118and/or to control a pressure of the reaction zone 110. Reaction zoneeffluent in line 118 can then feed to equipment (not shown) forisolating various streams (e.g., the desired oligomer) from the reactionzone effluent.

The catalyst system can flow through catalyst system feed line 152 fromthe catalyst system source 150 to combine with an optionally dispersedfeedstock mixture in line 192 (containing the ethylene, organic reactionmedium, the catalyst system, optionally hydrogen, and optionally the C₃₊olefin for a period of time). Joining line 152 and line 192 yieldscombined feed line 193, which in FIG. 3, can feed to the reaction zone110 via reaction zone inlet 119. Although FIG. 3 is described as flowinga pre-mixed or pre-prepared catalyst system to the reaction zone 110 vialines 152 and 193, an alternative aspect of the disclosed catalystsystems can be one where two of more of the components of the catalystsystem can be separately introduce/fed to the reaction zone where thecatalyst system is prepared in-situ within reaction zone 110 (as opposedto ex-situ mixing or preparation outside the reaction zone 110). Thatis, in an aspect of the disclosed reaction system, the catalyst systemcomponents can be introduced/fed separately to the reaction zone 110 orenter the system 300 at different points. For example, for a catalystsystem comprising i) a chromium component comprising a chromiumcompound, ii) a heteroatomic ligand, and iii) an aluminoxane, thechromium component and heteroatomic ligand can flow to the reaction zone110 via lines 152 and 193, while the aluminoxane can flow to thereaction zone 110 via one or more of: lines 172, 162, 191, 192, and 193;lines 162, 191, 192, and 193; lines 142, 191, 192, and 193; lines 191,192, and 193; lines 192 and 193; line 193; and directly to the reactionzone 110 via another line and/or another reaction zone inlet (notshown). For a catalyst system comprising i) a chromium componentcomprising a heteroatomic ligand chromium compound complex, and ii) analuminoxane, the chromium component can flow to the reaction zone 110via line 152, while the aluminoxane can flow to the reaction zone 110via one or more of: lines 172, 162, 191, 192, and 193; lines 162, 191,192, and 193; lines 142, 191, 192, and 193; lines 191, 192, and 193;lines 192 and 193; line 193; and directly to the reaction zone 110 viaanother line and/or another reaction zone inlet. The herein describedexamples are non-limiting and are only meant to describe possible waysthe catalyst system can be separately introduced/fed to the reactionzone 110 for the in-situ formation of the catalyst system within thereaction zone. Any description of line 152 in FIG. 3 as containing thecatalyst system herein can equally apply to aspects where only a part ofthe catalyst system is in line 152 while other parts are fed to thereaction zone 110 elsewhere in the system 300 and/or processesimplemented therein.

Alternatively (not shown), the catalyst system feed line 152 can combinewith the feedstock mixture in line 191, and the feedstock mixture feedline 191 (containing the ethylene, organic reaction medium, the catalystsystem, optionally hydrogen, and optionally for a period of time the C₃₊olefin) can flow directly to the reaction zone 110 via reaction zoneinlet 119 or can flow through mixing device 190 to yield a dispersedmixture (containing dispersed feedstock mixture, including ethylene, theorganic reaction medium, the catalyst system, optionally hydrogen, andoptionally for a period of time the C₃₊ olefin) which subsequently flowsto the reaction zone 110 via line 192 and reaction zone inlet 119.

Alternatively (not shown), the catalyst system feed line 152 can combinewith the organic reaction medium feed line 162. In such an aspect, theorganic reaction medium feed line 162 (containing the organic reactionmedium and catalyst system) can join with the ethylene feed line 142 toform the feedstock mixture feed line 191 comprising ethylene, organicreaction medium, catalyst system, optionally hydrogen, and optionallyfor a period of time the C₃₊ olefin. Line 191 which additionallyincludes the catalyst system can flow directly to the reaction zone 110via reaction zone inlet 119 or can flow through mixing device 190 toyield a dispersed feedstock mixture (containing ethylene, organicreaction medium, the catalyst system, optionally hydrogen, andoptionally for a period of time the C₃₊ olefin) which subsequently flowsto the reaction zone 110 via line 192 and reaction zone inlet 119.

In any of the above-described alternative catalyst system injectionaspects, the C₃₊ olefin for a period of time can combine with thecatalyst system feed line 152 prior to the catalyst system feed line 152joining with any of line 192 (e.g., via line 147 d shown FIG. 3), line191, line 162, or line 142.

The catalyst system feed line 152 can optionally include a solventand/or diluent along with the catalyst system. The solvent and/ordiluent can be any organic reaction medium described herein. In anembodiment, the solvent and/or diluent can be the organic reactionmedium utilized in the process. The catalyst system can be dispersed inthe solvent and/or diluent in the catalyst system feed line 152. Forexample, the catalyst system feed line 152 can include a mixing device(not shown), similar to mixing device 190 or in a precontactor apparatus(not shown), which is configured to disperse the catalyst system in thesolvent and/or diluent prior to the catalyst system combining with thedispersed ethylene feed stock mixture in line 192. When the solventand/or diluent and the catalyst system are present in the catalystsystem feed line 152 in FIG. 3, the chromium:diluent mass ratio can beany disclosed herein.

Organic reaction medium (optionally combined with the catalyst system)can flow in organic reaction medium feed line 162 from the organicreaction medium source 160, through the pump 180, and to the point wherethe ethylene feed line 142 and the organic reaction medium feed line 162join.

Similar to the system 200 of FIG. 2, at least a portion of the organicreaction medium in the system 300 of FIG. 3 can be contacted with ascrub agent (e.g., an alkylaluminum compound, any described herein)prior to introduction of the portion of the organic reaction medium tothe reaction zone 110. FIG. 3 shows scrub agent can be added via feedline 172 to the organic reaction medium feed line 162 such that theorganic reaction medium feed line 162 can contain both the organicreaction medium and the scrub agent. Alternatively, the scrub agent maynot be combined with the organic reaction medium in the organic reactionmedium feed line 162. The scrub agent is independently disclosed hereinand can be utilized to further described reaction system 300.

Likewise, similar to the system 200 of FIG. 2, at least a portion of theorganic reaction medium in the system 300 of FIG. 3 can be contactedwith the scrub agent (e.g., an alkylaluminum compound) prior to contactof the portion of organic reaction medium with ethylene. FIG. 3 showsthe co-catalyst can be added via line 172 to the organic reaction mediumfeed line 162, before the organic reaction medium contacts ethylene viacombination of the organic reaction medium feed line 162 with theethylene feed line 142. Alternatively, the scrub agent may not becombined with the organic reaction medium in the organic reaction mediumfeed line 162. The scrub agent is independently disclosed herein and canbe utilized to further described reaction system 300.

In FIG. 3, all of the organic reaction medium can be fed to the reactionzone via line 162. However, as is discussed herein, it is contemplatedthat only a portion of the total amount of organic reaction medium whichis used in the system 300 is in line 162 and optionally contacted withthe scrub agent prior to introduction/feeding to reaction zone 110:e.g., the other portions can be mixed with the catalyst system incatalyst system feed line 152 and/or can be included in a bypass linewhich can feed directly to the reaction zone 110. Alternatively, thescrub agent may not be combined with the organic reaction medium, andthe organic reaction medium feed line 162 can flow directly to thesuction side 181 of pump 180.

Ethylene (which can be optionally combined with the C₃₊ olefin for aperiod of time, and/or optionally hydrogen and/or the catalyst system)can flow in ethylene feed line 142 from the ethylene source 140 and cancombine with organic reaction medium (which is optionally previouslycombined with scrub agent, C₃₊ olefin, and/or catalyst system) flowingin line 162 on the head side 182 of the pump 180. Alternatively,ethylene can be combined with the organic reaction medium flowing inline 162 on the suction side 181 of the pump 180.

Combination of the ethylene in line 142 with the organic reaction mediumin line 162 yields a feedstock mixture in feedstock mixture line 191.The feedstock mixture flows through an optional mixing device 190 whereethylene and the organic reaction medium (which can be optionallypreviously combined with scrub agent and/or C₃₊ olefin) can bedispersed, and subsequently flow as a dispersed feedstock mixture indispersed feedstock mixture line 192.

The feedstock mixture can be contacted with the catalyst system prior tointroduction of the feedstock mixture into the reaction zone 110. InFIG. 3, the feedstock mixture in the form of dispersed feedstock mixturein line 192 can combine with the catalyst system in line 152 to form acombined feed line 193 which can flow to the reaction zone inlet 119 andfeeds to the reaction zone 110. Alternatively, the feedstock mixture canbe contacted with the catalyst system in line 152 via combination withline 191 and before the feedstock mixture enters the optional mixingdevice 190.

Hydrogen optionally can be used to control oligomerization reactions.The optional hydrogen can be fed into the ethylene feed line 142 ofreaction system 300 via hydrogen feed line 144. The combination ofhydrogen with ethylene in the ethylene feed line 144 can be upstream ofvalve 143 as shown in FIG. 3; or alternatively, downstream of valve 143.While the hydrogen feed line 144 in FIG. 3 is shown as feeding to theethylene feed line 142, it is contemplated that the hydrogen feed line144 can fluidly connect to any reaction zone inlet (e.g., reaction zoneinlet 115 or reaction zone inlet 119) directly or via another line(e.g., line 146, line 147 a, b, c, d, e, f, or g, line 152, line 162,line 172, line 191, line 192, or line 193).

The C₃₊ olefin can be introduced for a period of time to reaction system300 via any one or more of lines 147 a-g (the alternative nature beingshown as dashed lines in FIG. 3). For example, the C₃₊ olefin, which canbe introduced/fed for a period of time to the reaction zone, can flowfrom the C₃₊ olefin source 145 via line 146 and: i) via line 147 a tocombine with ethylene flowing in feed line 142, before ethylene joinswith organic reaction medium flowing in feed line 162 to form thefeedstock mixture in feedstock mixture line 191, ii) via line 147 b tocombine with the organic reaction medium flowing in line 162, before theorganic reaction medium joins with ethylene to form the feedstockmixture in line 191, iii) via line 147 c to add the C₃₊ olefin directlyto the reaction zone 110 via optional reaction zone inlet 115, iv) vialine 147 d to combine with the catalyst system flowing in line 152; v)via line 147 e to combine with the feedstock mixture flowing in line191, vi) via line 147 f to combine with the dispersed feedstock mixtureflowing in line 192, vii) via line 147 g to combine with the componentsof the combined feedstock mixture 193 before entry into the reactionzone 110 via reaction zone inlet 119, or viii) any combination ofi)-vii).

When introducing the C₃₊ olefin for a period of time via line 146 andline 147 a, the C₃₊ olefin can combine with ethylene flowing in ethylenefeed line 142. The ethylene feed line 142 (comprising ethylene, the C₃₊olefin, optionally hydrogen, and optionally catalyst system) can joinwith the organic reaction medium (which can be optionally previouslycombined with scrub agent) line 162 to form the feedstock mixture line191. That is, in an aspect where the C₃₊ olefin flows in line 147 a, thefeedstock mixture includes ethylene, organic reaction medium (which canbe optionally previously combined with scrub agent), and the C₃₊ olefin(and optionally hydrogen, and optionally the catalyst system). Thefeedstock mixture feed line 191 can flow into the mixing device 190where the components in line 191 are dispersed. The dispersed components(e.g., the dispersed feedstock mixture) can flow from the optionalmixing device 190 in the dispersed line 192. In aspects where thecatalyst system has not previously been joined to a line upstream of thereaction zone inlet 119, the components in dispersed line 192 can joinwith the catalyst system feed line 152 to form the combined feed line193 which contains the dispersed components of line 191 and the catalystsystem. Line 193 subsequently can flow to the reaction zone 110 via thereaction zone inlet 119. In the aspect where the C₃₊ olefin isintroduced via line 146 and line 147 a, the C₃₊ olefin can flow vialines 146, 147 a, 142, 191, 192, and 193 to the reaction zone 110.

When introducing the C₃₊ olefin for a period of time via line 146 andline 147 b, the C₃₊ olefin can combine with the organic reaction medium(which can be optionally previously combined with scrub agent) flowingin the organic reaction medium feed line 162. The organic reactionmedium line 162 (comprising the organic reaction medium, the C₃₊ olefin,and optionally catalyst system and/or optionally scrub agent) can joinwith the ethylene feed line 142 (comprising ethylene and optionallyhydrogen) to form the feedstock mixture line 191. That is, in an aspectwhere the C₃₊ olefin flows in line 147 b, the feedstock mixture in line191 includes ethylene, organic reaction medium, and the C₃₊ olefin(optionally scrub agent, optionally hydrogen, and/or optionally catalystsystem). The feedstock mixture feed line 191 can flow into the optionalmixing device 190 where the components in line 191 can be dispersed. Thedispersed components (e.g., the dispersed feedstock mixture) can flowfrom the optional mixing device 190 in the dispersed line 192. Inaspects where the catalyst system has not previously been joined to aline upstream of the reaction zone inlet 119, the components indispersed line 192 can join with the catalyst system feed line 152 toform the combined feed line 193 which contains the dispersed componentsof line 191 and the catalyst system. Line 193 subsequently can flow tothe reaction zone 110 via the reaction zone inlet 119. In the aspectwhere the C₃₊ olefin is introduced via line 146 and line 147 b, the C₃₊olefin can flow via lines 146, 147 b, 162, 191, 192, and 193 to thereaction zone 110.

When introducing the C₃₊ olefin for a period of time via line 146 andline 147 c, the C₃₊ olefin can flow directly to the reaction zone 110via the reaction zone inlet 115 which is configured to introduce the C₃₊olefin to the reaction zone 110.

When introducing the C₃₊ olefin for a period of time via line 146 andline 147 d, the C₃₊ olefin can combine with the catalyst system flowingin catalyst system feed line 152. In such an aspect, the catalyst systemcan flow for a period of time with the C₃₊ olefin in line 152 to joinwith the feedstock mixture outside the reaction zone 110. In FIG. 3,line 152 combines with the dispersed feedstock mixture in line 192 toform the combined feed stream 193, which flows to the reaction zone 110via the reaction zone inlet 119. In the aspect where the C3+ olefin isintroduced via line 146 and line 147 d, the C₃₊ olefin can flow vialines 146, 147 d, 152, and 193 to the reaction zone 110 via the reactionzone inlet 119.

When introducing the C₃₊ olefin for a period of time via line 146 andline 147 e, the C₃₊ olefin can combine with the feedstock mixture inline 191. The feedstock mixture feed line 191 can flow into the optionalmixing device 190 where the components (including C₃₊ olefin) in line191 can be dispersed. The dispersed components (e.g., the dispersedfeedstock mixture) can flow from the optional mixing device 190 indispersed line 192. In aspects where the catalyst system has notpreviously been joined to a line upstream of the reaction zone inlet119, the components in dispersed line 192 can join with the catalystsystem feed line 152 to form the combined feed line 193 which containsthe dispersed components of line 191 and the catalyst system. Line 193subsequently can flow to the reaction zone 110 via the reaction zoneinlet 119. In the aspect where the C₃₊ olefin can be introduced/fed fora period of time via line 146 and line 147 e, the C₃₊ olefin can flowvia lines 146, 147 e, 191, 192, and 193 to the reaction zone 110.

When introducing the C₃₊ olefin for a period of time via line 146 andline 147 f, the C₃₊ olefin can combine with the dispersed feedstockmixture in line 192. In such an aspect, the feedstock mixture enteringthe mixing device 190 can comprise ethylene and organic reaction medium(and optionally scrub agent, hydrogen, and/or catalyst system. Thedispersed components (e.g., the dispersed feedstock mixture) can flowfrom the optional mixing device 190 in dispersed line 192. Line 147 fcontaining the C₃₊ olefin can combine with dispersed line 192. Inaspects where the catalyst system has not previously been joined to aline upstream of the reaction zone inlet 119, the components (includingthe C₃₊ olefin) in dispersed line 192 can join with the catalyst systemfeed line 152 to form the combined feed line 193 which can contain thecomponents of line 192 (e.g., the dispersed feedstock mixture and C₃₊olefin) and the catalyst system. Line 193 subsequently can flow to thereaction zone 110 via the reaction zone inlet 119. In the aspect wherethe C₃₊ olefin is introduced via line 146 and line 147 f, the C₃₊ olefincan flow via lines 146, 147 f, 192, and 193 to the reaction zone 110.

When introducing the C₃₊ olefin for a period of time via line 146 andline 147 g, the C₃₊ olefin can combine with the combined feed componentsin combined feed line 193. In the aspect where the C₃₊ olefin for aperiod of time can be introduced/fed via line 146 and line 147 g, theC₃₊ olefin can flow via lines 146, 147 g, and 193 to the reaction zone110.

With respect to the commencement of the flow of the C₃₊ olefin relativeto the commencement of the flow of ethylene for the period of time, theflow of C₃₊ olefin can commence before or simultaneously with the flowof ethylene regardless which of lines 147 a, 147 b, 147 c, 147 d, 147 e,147 f, and/or 147 g the C₃₊ olefin flows. Alternatively, the flow of theC₃₊ olefin can commence before the flow of ethylene (when the reactionzone 110 is empty, for example, during hard startup, or when thereaction zone 110 already contains material, for example, in a softstartup after temporary cessation of the flow of ethylene and/orcatalyst system to the reaction zone 110 to address process or systemissues), then be stopped temporarily, and then again commenced before orat the same time (simultaneously) as the flow of ethylene and/orcatalyst system.

With respect to the commencement of the flow of the C₃₊ olefin relativeto the commencement of the flow of catalyst system for the period oftime, the flow of the C₃₊ olefin can commence before, simultaneously, orafter the flow of the catalyst system regardless of which lines 147 a,147 b, 147 c, 147 d, 147 e, 147 f, and/or 147 g the C₃₊ olefin flows.

With respect to the commencement of the flow of the C₃₊ olefin relativeto the commencement of the flow of organic reaction medium for theperiod of time, the flow of the C₃₊ olefin can commence before,simultaneously, or after the flow of the organic reaction mediumregardless of which lines 147 a, 147 b, 147 c, 147 d, 147 e, 147 f,and/or 147 g the C₃₊ olefin flows.

With respect to the commencement of the flow of the C₃₊ olefin relativeto the commencement of the flow of scrub agent for the period of time,the flow of the C₃₊ olefin can commence before, simultaneously, or afterthe flow of the scrub agent regardless of which lines 147 a, 147 b, 147c, 147 d, 147 e, 147 f, and/or 147 g the C₃₊ olefin flows.

Reaction zone 110 in FIGS. 1-3 is shown as a single continuousstirred-tank reactor operating in continuous mode with a continuousstirred-tank configuration. Various alternative configurations and/oroperating modes that can achieve desired ethylene oligomerizationresults are contemplated for the reaction zone 110 and are discussed inmore detail herein. In FIGS. 1-3, thermocouple 114 can read thetemperature of the reaction zone 110 as the reaction proceeds. Stirrer116 of FIGS. 1-3 operated by motor 112 can agitate the contents of thereaction zone 110. The stirrer 116 of FIGS. 1-3 can be an impellercoupled to the motor 112 via a rod. Heat exchanger 120 of FIGS. 1-3 canreceive line 122 and can provide line 124 to the reaction zone 110 inorder to maintain a temperature of the reaction zone 110.

A reaction zone effluent comprising an ethylene oligomer product formedin the reaction zone 110 in FIGS. 1-3 can flow in line 118 from reactionzone outlet 117. In some embodiments, the ethylene oligomer product inline 118 can flow to the product recovery zone (not shown). The productrecovery zone can include catalyst system deactivation, an oligomerproduct separation where the ethylene oligomer product (e.g., hexenesand/or octenes) can be recovered from the reaction zone effluent viatechniques known in the art with the aid of this disclosure (e.g.,distillation, flashing, absorption, stripping), by-product separationand/or isolation, and/or any steps which can facilitate the handling ofthe reaction zone effluent and the isolation of the desired ethyleneoligomers.

The reaction zone of any process, system and/or reaction system (e.g.,reaction zone 110 of the figures) can comprise any reactor which canoligomerize ethylene to an ethylene oligomer product. In an embodiment,the reaction zone of any process, system, or reaction system describedherein can comprise a stirred tank reactor, a plug flow reactor, or anycombination thereof; alternatively, a stirred tank reactor; oralternatively, a plug flow reactor. In an embodiment, the reaction zoneof any process, system, or reaction system described herein can comprisean autoclave reactor, a continuous stirred tank reactor, a loop reactor,a gas phase reactor, a solution reactor, a tubular reactor, a recyclereactor, a bubble reactor, or any combination thereof; alternatively, anautoclave reactor; alternatively, a stirred tank reactor; alternatively,a loop reactor; alternatively, a gas phase reactor; alternatively, asolution reactor; alternatively, a tubular reactor; alternatively, arecycle reactor; or alternatively, a bubble reactor. In someembodiments, the reaction zone can comprise multiple reactor; oralternatively, only on reactor. When multiple reactors are present, eachof the reactors can be the same or different types of reactors. Thereaction zone (e.g., reaction zone 110) can comprise single or multiplereactors of any of the types disclosed herein operating in batch orcontinuous mode; alternatively, continuous mode.

Aspects and/or embodiments of the processes, systems, and/or reactionsystems described herein can utilize a pump. In an embodiment, the pumpcan be any pump which can pump the organic reaction medium to thereaction zone. Generally, the pump can have a suction side whichreceives the organic reaction medium and a head side which provides theorganic reaction medium at a pressure suitable for flow to the reactionzone. FIG. 1, FIG. 2, and FIG. 3 provide non-liming examples of reactionsystems which can utilize a pump 180 having suction side 181 and headside 182. In FIG. 1, pump 180 is in fluid communication with thereaction zone inlet 215. In FIG. 2, pump 180 is in fluid communicationwith the reaction zone inlet 113. In FIG. 3, pump 180 is in fluidcommunication with reaction zone inlet 119. FIG. 1, FIG. 2, and FIG. 3show that pump 180 can be located upstream of the point where ethylene(e.g., from the ethylene feed line 142) and the organic reaction medium(e.g., from the organic reaction medium feed line 162 which optionallycontains scrub agent and/or catalyst system) join/combine to form thefeedstock mixture. Feeding ethylene in this configuration can reduceflashing and recompression. In an embodiment, the pump 180 can beconfigured to receive the catalyst system and/or the scrub agentcombined with the organic reaction medium on the suction side 181 of thepump 180; alternatively, the catalyst system and/or the scrub agent canbe combined with the organic reaction medium on the head side 182 of thepump 180; alternatively, the catalyst system can be combined with theorganic reaction medium on the suction side 181 of the pump 180 whilethe scrub agent can be combined with the organic reaction medium andcatalyst system on the head side 182 of the pump; alternatively, thescrub agent can be combined with the organic reaction medium on thesuction side 181 of the pump 180 while the catalyst system can becombined with the organic reaction medium and scrub agent on the headside 182 of the pump 180. In the system 300 in FIG. 3, pump 180 can beconfigured to receive the catalyst system combined with the organicreaction medium on the suction side 181 and to pump the catalyst systemcombined with the organic reaction medium and optional scrub agent onthe head side 182 of the pump 180.

In configurations where the reaction zone 110 has a recycle features, apump can be included in the path of the reaction zone 110 suitable forpassing contents of the reaction zone 110 to heat exchangers. Forexample a pump suitable for pumping reaction zone contents can be placedin line 122 of FIG. 1, FIG. 2, or FIG. 3 to pass the contents to theheat exchanger 120.

Aspects and/or embodiments of the processes, systems, and/or reactionsystems described herein can utilize a mixing device to mix/disperse theethylene and the organic reaction medium. In an embodiment, the mixingdevice can be any device which can mix/disperse the organic reactionmedium and ethylene in the feedstock mixture. Such mixing/dispersing canbe implemented to minimize areas of high ethylene concentration withinthe feedstock mixture. The mixing device can provide mixing of ethyleneand the organic reaction medium via agitation of the flow there through.For example, the mixing device can be a static mixer having fixedbaffles (e.g., in a helical arrangement, or any other bafflearrangement) placed within a housing, where the baffles continuouslyblend the ethylene and organic reaction medium to disperse the ethyleneand the organic reaction medium in the feedstock mixture. Alternatively,the mixing device can have moving parts such as a propeller or impeller.FIG. 1 shows an optional mixing device 190 that can be positionedbetween i) the joining of the ethylene feed line 142 and the organicreaction medium feed line 162 and ii) the second reaction zone inlet 113such that ethylene and the organic reaction medium are dispersed in thefeedstock mixture prior to the feedstock mixture entering the reactionzone 110. FIG. 2 shows an optional mixing device 190 can be positionedbetween i) the joining of the ethylene feed line 142 and the organicreaction medium feed line 162 and ii) the reaction zone inlet 119 suchthat ethylene and the organic reaction medium are dispersed in thefeedstock mixture prior to the ethylene feedstock combining with thecatalyst system and prior to the feedstock mixture entering the reactionzone 110. In some embodiments, the mixing/dispersion of the ethylene andthe organic reaction medium can be accomplished using a precontactordevice such a vessel with a mixing device.

Lines 118, 122, 124, 142, 146, 147 a-g, 152, 162, 172, 191, 192, and 193shown in the figures can be appropriate metal piping or tubing forethylene oligomerization reaction system components.

The reaction zone inlets 111, 113, 115, 119, 213, and 215 as well as thereaction zone outlet 117, shown in the figures can be in the form offlanges and/or appropriate piping and valves for receiving the variousfeed components and removing the reaction zone effluent from thereaction zone 110. The reaction zone outlet 117 can be one or morephysical outlets. For example, the reaction zone 110 shown in FIG. 1,FIG. 2, and FIG. 3 can have one outlet 117; alternatively, the reactionzone 110 can have one or more other outlets in addition to outlet 117;alternatively, the reaction zone 110 can include multiple reactors, eachhaving a single outlet or multiple outlets which amount to more than oneoutlet for the collection of multiple reactors which define the reactionzone 110. Additionally, each reaction zone inlet which is shown as asingle reaction zone inlet can represent one or more reaction inletsfeeding the designated materials to the reaction zone.

Ethylene for any of the processes, systems, and/or reaction systemsdescribed herein (e.g., ethylene source 140) can be oligomerization orpolymerization grade ethylene. By “oligomerization or polymerizationgrade ethylene” it is meant that ethylene is present in ethylene feedline 142 in an amount of at least 98.0, 98.5, 99.0, 99.1, 99.2, 99.3,99.4, 99.5, 99.6, 99.7, 99.8, 99.9, 99.99, 99.999 mol % based on thetotal moles of components in the ethylene composition (e.g., ethylenefeed line 142). The ethylene for any of the processes, systems, and/orreaction systems (e.g., ethylene source 140) can be any source ofoligomerization or polymerization grade ethylene, for example, a storagetank or a line from a cracking process, monomer recovery process, andthe like. In an embodiment of the processes, systems, and/or reactionsystems (e.g., reaction systems 100, 200, and 300) disclosed herein,substantially all of the ethylene used in the disclosed processes,systems, and/or reaction systems (e.g., reaction systems 100, 200, and300) can be contacted with the catalyst system and/or introduced/fed tothe reaction zone via the feedstock mixture. By “substantially all” itis meant that at least 99.0, 99.1, 99.2, 99.3, 99.4, 99.5, 99.6, 99.7,99.8, 99.9, 99.99, 99.999 mol % of the total ethylene used by theprocesses, systems, and/or reactions systems (e.g. reaction systems 100,200, or 300) described herein can be introduced/fed to the reaction zonevia the feedstock mixture.

The C₃₊ olefin can be one or a combination of olefins having three ormore carbon atoms. In an aspect, the C₃₊ olefin can be a C₃ to C₁₈olefin, a C₄ to C₁₄ olefin, or a C₆ to C₁₂ olefin. In an embodiment, anyolefin which can be utilized in the processes, systems, and/or reactionsystems described herein can be an internal olefin, or an alpha olefin.In some embodiments, the internal olefin or alpha olefin can be branchedor linear; alternatively, branched; or alternatively, linear. In someembodiments, as the C₃₊ olefin any olefin which can be utilized in theprocesses, systems, and/or reaction systems described herein can be anormal alpha olefin. Suitable non-limiting examples of the C₃₊ olefininclude one or more of propylene, butene, pentene, hexene, heptene,octene, nonene, decene, undecene, dodecene, tridecene, tetradecene,pentadecene, hexadecene, heptadecene, octadecene, or any combinationthereof. In an embodiment, the C₃₊ olefin can comprise iso-butene. In anembodiment , the C₃₊ olefin can comprise, or consist essentially of,propene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene,1-tetradecene, 1-hexedecene, 1-octacene, or any combination thereof;alternatively, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene,1-tetradecene, or any combination thereof; alternatively, 1-hexene,1-octene, 1-decene, 1-docene, or any combination thereof; alternatively,1-hexene, 1-octene, or any combination thereof; alternatively, propene;alternatively, 1-butene; alternatively, 1-hexene; alternatively,1-octene; alternatively, 1-decene; or alternatively, 1-dodecene. The C₃₊olefin source 145 can be any source of olefins having 3 or more carbonatoms, including a recycle line which flows a C₃₊ olefin recovered froman oligomer product to the C₃₊ olefin feed line 146.

The processes, systems, and/or reaction systems described herein can usean organic reaction medium. Generally, the organic reaction can act as asolvent or a diluent in the processes described herein. In an aspect,the organic reaction medium can be a hydrocarbon, a halogenatedhydrocarbon, or a combination thereof, for example. Hydrocarbons andhalogenated hydrocarbons which can be used as an organic reaction mediumcan include, for example, aliphatic hydrocarbons, aromatic hydrocarbons,petroleum distillates, halogenated aliphatic hydrocarbons, halogenatedaromatic hydrocarbons, or combinations thereof. Aliphatic hydrocarbonswhich can be useful as an organic reaction medium include C₃ to C₂₀aliphatic hydrocarbons, or C₄ to C₁₅ aliphatic hydrocarbons, or C₅ toC₁₀ aliphatic hydrocarbons, for example. The aliphatic hydrocarbonswhich can be used as an organic reaction medium can be cyclic or acyclicand/or can be linear or branched, unless otherwise specified.Non-limiting examples of suitable acyclic aliphatic hydrocarbon organicreaction mediums that can be utilized singly or in any combinationinclude propane, iso-butane, n-butane, butane (n-butane or a mixture oflinear and branched C₄ acyclic aliphatic hydrocarbons), pentane(n-pentane or a mixture of linear and branched C₅ acyclic aliphatichydrocarbons), hexane (n-hexane or mixture of linear and branched C₆acyclic aliphatic hydrocarbons), heptane (n-heptane or mixture of linearand branched C₇ acyclic aliphatic hydrocarbons), octane (n-octane or amixture of linear and branched C₈ acyclic aliphatic hydrocarbons), orcombinations thereof. Non-limiting examples of suitable cyclic aliphatichydrocarbons which can be used as an organic reaction medium includecyclohexane, and methyl cyclohexane, for example. Aromatic hydrocarbonswhich can be useful as an organic reaction medium include C₆ to C₁₀aromatic hydrocarbons. Non-limiting examples of suitable aromatichydrocarbons that can be utilized singly or in any combination as anorganic reaction medium include benzene, toluene, xylene (includingortho-xylene, meta-xylene, para-xylene, or mixtures thereof),ethylbenzene, or combinations thereof. Halogenated aliphatichydrocarbons which can be useful as an organic reaction medium includeC₁ to C₁₅ halogenated aliphatic hydrocarbons, C₁ to C₁₀ halogenatedaliphatic hydrocarbons, or C₁ to C₅ halogenated aliphatic hydrocarbons,for example. The halogenated aliphatic hydrocarbons which can be used asan organic reaction medium can be cyclic or acyclic and/or can be linearor branched, unless otherwise specified. Non-limiting examples ofsuitable halogenated aliphatic hydrocarbons which can be utilized as anorganic reaction medium include methylene chloride, chloroform, carbontetrachloride, dichloroethane, trichloroethane, and combinationsthereof. Halogenated aromatic hydrocarbons which can be useful as anorganic reaction medium include C₆ to C₂₀ halogenated aromatichydrocarbons, or C₆ to C₁₀ halogenated aromatic hydrocarbons, forexample. Non-limiting examples of suitable halogenated aromatichydrocarbons which can be used as a solvent include chlorobenzene,dichlorobenzene, or combinations thereof, for example.

The choice of organic reaction medium can be made on the basis ofconvenience in processing. For example, isobutane can be chosen to becompatible with solvents and diluents used in processes using theproduct(s) of the process described herein (e.g., using the product forthe formation of polymer in a subsequent processing step). In someembodiments, the organic reaction medium can be chosen to be easilyseparable from the one or more of the oligomer in the ethylene oligomerproduct. In some embodiments, an oligomer of the ethylene oligomerproduct can be utilized as the reaction system solvent. For example,when 1-hexene is an oligomer of an ethylene trimerization process,1-hexene can be chosen as the reaction system solvent to decrease theneed for separation.

The organic reaction medium source (e.g., organic reaction medium source160) can be any source for an organic reaction medium, including astorage tank of the organic reaction medium and any line from anoligomerization process, a polymerization process, monomer recoveryprocess, and the like.

While in FIG. 1, FIG. 2, and FIG. 3 the entire supply of organicreaction medium is shown flowing in line 162 from the organic reactionmedium source 160 to the reaction zone 110, it is contemplated that onlya portion of the total amount of organic reaction medium used in systems100, 200, and 300 flows in line 162, and that a bypass line can bealternatively utilized to flow another portion of the organic reactionmedium (e.g., a portion which is not combined with any other reactioncomponent) directly to the reaction zone 110 and in parallel flow toline 162. Additionally or alternatively, a portion of the total amountof organic reaction medium in the system 100, 200, or 300 can beutilized in the catalyst system feed line 152. That is, a portion of theorganic reaction medium can be used to dilute or act as a carrying fluidfor the catalyst system in catalyst system feed line 152.

As described herein, aspects and embodiments of the disclosed processes,systems and/or reaction systems can include combining ethylene and anorganic reaction medium to form a feedstock mixture. The minimumethylene concentration in the feedstock mixture can be 4 mass %, 10 mass%, 25 mass %, 35 mass %, or 40 mass % based upon the total mass in thefeedstock mixture; alternatively or additionally, at a maximum ethyleneconcentration of the feedstock mixture cam be 65 mass %, 60 mass %, 55mass %, 50 mass %, 48 mass % based upon the total mass in the reactionzone. In an embodiment, ethylene concentration in the feedstock mixturecan from any minimum ethylene concentration in the feedstock mixturedisclosed herein to any maximum ethylene concentration in the feedstockmixture disclosed herein. In some non-limiting embodiments, the ethyleneconcentration in the feedstock mixture can be in a range of from 4 mass% to 60 mass %, from 10 mass % to 60 mass %, from 25 mass % to 55 mass%, 35 mass % to 50 mass %, or 40 mass % to 48 mass % based upon thetotal mass in the reaction zone. Other ethylene concentrations in thefeedstock mixture ranges that can be utilized are readily apparent tothose skilled in the art with the aid of this disclosure.

Aspects and embodiments of the herein described processes, systems,and/or reaction systems can utilize a catalyst system comprising i) achromium component comprising a chromium compound, ii) a heteroatomicligand, and iii) an aluminoxane; or alternatively, i) a chromiumcomponent comprising a heteroatomic ligand chromium compound complex,and ii) an aluminoxane. Generally, the chromium compound, theheteroatomic ligand, the heteroatomic ligand chromium compound complex,the aluminoxane, and any other element of the catalyst system describedherein are independent elements of their respective catalyst systems.These catalyst system elements are independently described herein andcan be utilized without limitation, and in any combination, to furtherdescribe catalyst system utilized in aspects and/or embodiments of theprocesses, systems, and/or reaction systems described herein.

Generally, the chromium compound or the chromium compound of theheteroatomic ligand chromium compound complexes described herein canhave formula CrX_(p) where X represents a monoanionic ligand, and prepresent the number of monoatomic ligands (and the oxidation state ofthe chromium in the chromium compound. The monoanionic ligand (X), and pare independent elements of the chromium compound or the chromiumcompound of the heteroatomic ligand chromium compound complexesdescribed herein and are independently described herein. The independentdescriptions of the monoanionic ligand (X) and p can be utilized withoutlimitation, and in any combination, to further describe the chromiumcompound or the chromium compound of the heteroatomic ligand chromiumcompound complexes described herein.

Generally, the chromium atom of the chromium compound or the chromiumcompound of the heteroatomic ligand chromium compound complexesdescribed herein can have any positive oxidation state available to achromium atom. In an embodiment, the chromium atom can have an oxidationstate of from +2 to +6; alternatively, from +2 to +4; or alternatively,from +2 to +3. In some embodiments, the chromium atom of the chromiumcompound or the chromium compound of the heteroatomic ligand chromiumcompound complexes described herein can have an oxidation state of +1;alternatively, +2; alternatively, +3; or alternatively, +4.

The monoanion, X, of the chromium compound or the chromium compound ofthe heteroatomic ligand chromium compound complexes described herein canbe any monoanion. In an embodiment, the monoanion, X, can be a halide, acarboxylate, a β-diketonate, a hydrocarboxide, a nitrate, or a chlorate.In some embodiments, the monoanion, X, can be a halide, a carboxylate, aβ-diketonate, or a hydrocarboxide. In any aspect or embodiment, thehydrocarboxide can be an alkoxide, an aryloxide, or an aralkoxide.Generally, hydrocarboxide (and subdivisions of hydrocarboxide) are theanion analogues of the hydrocarboxy group. In other embodiments, themonoanion, X, can be a halide, a carboxylate, a β-diketonate, or analkoxide; or alternatively, a halide or a β-diketonate. In otherembodiments, the monoanion, X, can be a halide; alternatively, acarboxylate; alternatively, a β-diketonate; alternatively, ahydrocarboxide; alternatively, an alkoxide; or alternatively, anaryloxide. Generally, the number, p, of monoanions can equal theoxidation state of the metal atom. In an embodiment, the number, p, ofmonoanions, X, can be from 2 to 6; alternatively, from 2 to 4;alternatively, from 2 to 3; alternatively, 1; alternatively, 2;alternatively, 3; or alternatively, 4.

Generally, each halide monoanion, X, of the chromium compound or thechromium compound of the heteroatomic ligand chromium compound complexesdescribed herein independently can be fluorine, chlorine, bromine, oriodine; or alternatively, chlorine, bromine, or iodine. In anembodiment, each halide monoanion, X, of the chromium compound or thechromium compound of the heteroatomic ligand chromium compound complexesdescribed herein can be chlorine; alternatively, bromine; oralternatively, iodine.

Generally, each carboxylate monoanion of the chromium compound or thechromium compound of the heteroatomic ligand chromium compound complexesdescribed herein independently can be a C₁ to C₂₀ carboxylate; oralternatively, a C₁ to C₁₀ carboxylate. In an embodiment, eachcarboxylate monoanion of the chromium compound or the chromium compoundof the heteroatomic ligand chromium compound complexes described hereinindependently can be acetate, a propionate, a butyrate, a pentanoate, ahexanoate, a heptanoate, an octanoate, a nonanoate, a decanoate, anundecanoate, or a dodecanoate; or alternatively, a pentanoate, ahexanoate, a heptanoate, an octanoate, a nonanoate, a decanoate, anundecanoate, or a dodecanoate. In some embodiments, each carboxylatemonoanion of the chromium compound or the chromium compound of theheteroatomic ligand chromium compound complexes described hereinindependently can be acetate, propionate, n-butyrate, valerate(n-pentanoate), neo-pentanoate, capronate (n-hexanoate), n-heptanoate,caprylate (n-octanoate), 2-ethylhexanoate, n-nonanoate, caprate(n-decanoate), n-undecanoate, or laurate (n-dodecanoate); alternatively,valerate (n-pentanoate), neo-pentanoate, capronate (n-hexanoate),n-heptanoate, caprylate (n-octanoate), 2-ethylhexanoate, n-nonanoate,caprate (n-decanoate), n-undecanoate, or laurate (n-dodecanoate);alternatively, capronate (n-hexanoate); alternatively, n-heptanoate;alternatively, caprylate (n-octanoate); or alternatively,2-ethylhexanoate. In some embodiments, the carboxylate monoanion of thechromium compound or the chromium compound of the heteroatomic ligandchromium compound complexes described herein can be triflate(trifluoroacetate).

Generally, each β-diketonate monoanion of the chromium compound or thechromium compound of the heteroatomic ligand chromium compound complexindependently can be any C₁ to C₂₀ a β-diketonate; or alternatively, anyC₁ to C₁₀ β-diketonate. In an embodiment, each β-diketonate monoanion ofthe chromium compound or the chromium compound of the heteroatomicligand chromium compound complexes described herein independently can beacetylacetonate (i.e., 2,4-pentanedionate), hexafluoroacetylacetone(i.e., 1,1,1,5,5,5-hexafluoro-2,4-pentanediuonate), orbenzoylacetonate); alternatively, acetylacetonate; alternatively,hexafluoroacetylacetone; or alternatively, benzoylacetonate.

Generally, each hydrocarboxide monoanion of the chromium compound or thechromium compound of the heteroatomic ligand chromium compound complexesdescribed herein independently can be any C₁ to C₂₀ hydrocarboxide; oralternatively, any C₁ to C₁₀ hydrocarboxide. In an embodiment, eachhydrocarboxide monoanion of the chromium compound or the chromiumcompound of the heteroatomic ligand chromium compound complexesdescribed herein independently can be a C₁ to C₂₀ alkoxide;alternatively, a C₁ to C₁₀ alkoxide; alternatively, a C₆ to C₂₀aryloxide; or alternatively, a C₆ to C₁₀ aryloxide. In an embodiment,each alkoxide monoanion of the chromium compound or the chromiumcompound of the heteroatomic ligand chromium compound complexesdescribed herein independently can be methoxide, ethoxide, a propoxide,or a butoxide. In some embodiments, each alkoxide monoanion of thechromium compound or the chromium compound of the heteroatomic ligandchromium compound complexes described herein independently can bemethoxide, ethoxide, isopropoxide, or tert-butoxide; alternatively,methoxide; alternatively, an ethoxide; alternatively, an iso-propoxide;or alternatively, a tert-butoxide. In an aspect, the aryloxide can bephenoxide.

In a non-limiting embodiment, the chromium compound or the chromiumcompound of the heteroatomic ligand chromium compound complex cancomprise, can consist essentially of, or consist of, a chromium(II)halide, a chromium(III) halide, a chromium(II) carboxylate,chromium(III) carboxylate, a chromium(II) β-diketonate, or achromium(III) β-diketonate. In some non-limiting embodiments, thechromium compound or the chromium compound of the heteroatomic ligandchromium compound complex can consist essentially of, or consist of, achromium(II) halide, a chromium(II) carboxylate, or a chromium(II)β-diketonate; or alternatively, a chromium(III) halide, a chromium(III)carboxylate, or a chromium(III) β-diketonate. In other non-limitingembodiments, the chromium compound or the chromium compound of theheteroatomic ligand chromium compound complex can comprise, can consistessentially of, or consist of, a chromium(II) halide; alternatively, achromium(III) halide; alternatively, a chromium (II) carboxylate;alternatively, a chromium(III) carboxylate; alternatively, achromium(II) β-diketonate; or alternatively, a chromium(III)β-diketonate.

In a non-limiting embodiment, the chromium compound or the chromiumcompound of the heteroatomic ligand chromium compound complexesdescribed herein can comprise, can consist essentially of, or consistof, chromium(II) chloride, chromium(III) chloride, chromium(II)fluoride, chromium(III) fluoride, chromium(II) bromide, chromium(III)bromide, chromium(II) iodide, chromium(III) iodide, chromium(II)acetate, chromium(III) acetate, chromium(II) 2-ethylhexanoate,chromium(III) 2-ethylhexanoate, chromium(II) triflate, chromium(III)triflate, chromium(II) nitrate, chromium(III) nitrate, chromium(II)acetylacetonate, chromium(III) acetylacetonate, chromium(II)hexafluoracetylacetonate, chromium(III) hexafluoracetylacetonate,chromium(III) benzoylacetonate, or chromium(III) benzoylacetonate. Insome non-limiting embodiments, the chromium compound or the chromiumcompound of the heteroatomic ligand chromium compound complexesdescribed herein can comprise, can consist essentially of, or consistof, chromium(III) chloride, chromium(III) fluoride, chromium(III)bromide, chromium(III) iodide, chromium(III) chloride (THF) complex,chromium(III) acetate, chromium(III) 2-ethylhexanoate, chromium(III)triflate, chromium(III) nitrate, chromium(III) acetylacetonate,chromium(III) hexafluoracetylacetonate, or chromium(III)benzoylacetonate. In further embodiments, the chromium compound or thechromium compound of the heteroatomic ligand chromium compound complexesdescribed herein described herein can be chromium(III) chloride, orchromium(III) acetylacetonate; alternatively, chromium(III) chloride; oralternatively, chromium(III) acetylacetonate.

In an embodiment, the heteroatomic ligand or the heteroatomic ligand ofthe heteroatomic ligand chromium compound complex can have the formula(R^(1s))_(m)X^(1a)(L^(1s))X^(1s)(R^(1s))_(n) while the heteroatomicligand of the heteroatomic ligand chromium compound complex can have theformula:

In some embodiments, the heteroatomic ligand or the heteroatomic ligandof the heteroatomic ligand chromium compound complex can have two groupscapable of being described by the formula(R^(1s))_(m)X^(1a)(L^(1s))X^(1s)(R^(1s))_(n). In instances wherein theheteroatomic ligand can have two groups capable of being described bythe formula (R^(1s))_(m)X^(1a)(L^(1s))X^(1s)(R^(1s))_(n), the twoL^(1s)groups are linked and the heteroatomic ligand and the heteroatomicligand chromium compound complex can have the formulas:

respectively.

In the heteroatomic ligand or the heteroatomic ligand of theheteroatomic ligand chromium compound complex having formula(R^(1s))_(m)X^(1a)(L^(1s))X^(1s)(R^(1s))_(n) or having two linked(R^(1s))_(m)X^(1a)(L^(1s))X^(1s)(R^(1s))_(n) groups, each X^(1s) andeach X^(2s) is independently selected from the group consisting of N, P,O, and S; each L^(1s) is an independent linking group between therespective X^(1s)s and X^(2s)s; each m and each n are independently 1 or2; and each R^(1s) and each R^(2s) are independently hydrogen, anorganyl group (or alternatively, an organyl group consisting essentiallyof inert functional group; or alternatively, a hydrocarbyl group), or aheterohydrocarbyl group, where when there are two or more R^(1s)s and/ortwo R^(2s)s, each R^(1s) can be the same or different (alternatively,the same; or alternatively, different) and/or each R^(2s) can be thesame or different (alternatively, the same; or alternatively,different). Additionally, in the heteroatomic ligand chromium compoundcomplex, X is a monoanionic ligand and p is the number of monoanionicligands in the heteroatomic ligand chromium compound complex. L^(1s),X^(1s), X^(2s), R^(1s), R^(2s), m, and n are independent elements of anyheteroatomic ligand or any heteroatomic ligand of the heteroatomicligand chromium compound complex which have an L^(1s), X^(1s), X^(2s),R^(1s), R^(2s), m, and/or n and are independently described herein.These independent descriptions of L^(1s), X^(1s), X^(2s), R^(1s),R^(2s), m, and n can be utilized without limitation, and in anycombination, to further describe any heteroatomic ligand or anyheteroatomic ligand of the heteroatomic ligand chromium compound complexwhich have an L^(1s), X^(1s), X^(2s), R^(1s), R^(2s), m, and/or n.Additionally, X and p are independent elements of the chromium compoundof the heteroatomic ligand chromium compound complex, are independentlydescribed herein, and can be utilized without limitation, and in anycombination, to further describe the chromium compound of theheteroatomic ligand chromium compound complex, and can be utilizedwithout limitation, and in any combination with L^(1s), X^(1s), X^(2s),R^(1s), R^(2s), m, and n of the heteroatomic ligand to further describethe heteroatomic ligand chromium compound complexes contemplated herein.

Each X^(1s) and each X^(2s) of any heteroatomic ligand described hereinor any heteroatomic ligand of any heteroatomic ligand chromium compoundcomplex described herein having an X^(1s) and/or X^(2s) can beindependently selected from N, P, O, and S; alternatively, independentlyselected from N and P; or alternatively, independently selected from Oand S. In some embodiments, each X^(1s) and each X^(2s) can be N;alternatively, P; alternatively O; or alternatively S. Each m and each nof any heteroatomic ligand described herein or any heteroatomic ligandof any heteroatomic ligand chromium compound complex described hereinhaving an m and/or n can be independently selected from 1 or 2;alternatively, 1; or alternatively, 2. Is some particular embodiments,each m and/or each n can be 1 when X^(1s) and/or X^(2s), respectively,is O or S; alternatively, O; or alternatively, S. In some otherparticular embodiments, each m and/or each n can be 2 when X^(1s) and/orX^(2s), respectively, is N or P; alternatively, N; or alternatively, P.

In a non-limiting embodiment, the heteroatomic ligand can have theformula R^(1s)S(L^(1s))SR^(1s), (R^(1s))₂P(L^(1s))P(R^(1s))₂, or(R^(1s))₂N(L^(1s))N(R^(1s))₂; alternatively, R^(1s)S(L^(1s))SR^(1s)_(n); alternatively, (R^(1s))₂P(L^(1s))P(R^(1s))₂; or alternatively,(R^(1s))₂N(L^(1s))NP(R^(1s))₂ while heteroatomic ligand chromiumcompound complex can have any one of the formulas.

In non-limiting embodiments where the heteroatomic ligand or theheteroatomic ligand of the heteroatomic ligand chromium compound complexhas two linked heteroatomic groups, the heteroatomic ligand can have theformula selected from one or more of

while the heteroatomic ligand chromium compound complex can have any oneof the formulas

In an embodiment, each L^(1s) of any heteroatomic ligand describedherein or any heteroatomic ligand of the heteroatomic ligand chromiumcompound complex described herein independently can be any group capableof linking group X^(1s) and X^(2s). In some embodiments, each L^(2s)independently can be an organylene group, an amin-di-yl group, or aphosphin-di-yl group; alternatively, an organylene group consisting ofinert functional groups, an amin-di-yl group, or a phosphin-di-yl group;alternatively, a hydrocarbylene group, an amin-di-yl group, or aphosphin-di-yl group; alternatively an amin-di-yl group or aphosphin-di-yl group; alternatively, an organylene group; alternatively,an organylene group consisting of inert functional groups;alternatively, a hydrocarbylene group; alternatively, an amin-di-ylgroup; or alternatively, a phosphin-di-yl group. In an embodiment, theL^(1s) organylene group that can be utilized as L^(1s) can be a C₁ toC₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or, a C₁ to C₅ organylene group. In anembodiment, the L^(1s) organylene group consisting of inert functionalgroups that can be utilized as L^(1s) can be a C₁ to C₂₀, a C₁ to C₁₅, aC₁ to C₁₀, or, a C₁ to C₅ organylene group consisting of inertfunctional groups. In an embodiment, the L^(1s) hydrocarbylene groupthat can be utilized as L^(1s) can be a C₁ to C₂₀, a C₁ to C₁₅, a C₁ toC₁₀, or a C₁ to C₅ hydrocarbylene group. In an embodiment, theamin-di-yl group that can be utilized as L^(1s) can be a C₁ to C₃₀, a C₁to C₂₀, a C₁ to C₁₅, or a C₁ to C₁₀ amin-di-yl group. In an embodiment,the phosphin-di-yl group that can be utilized as L^(1s) can be a C₁ toC₃₀, a C₁ to C₂₀, a C₁ to C₁₅, or a C₁ to C₁₀ phosphin-di-yl group.

In an embodiment, the each organylene L^(1s) group can have the formula-(L^(3s))NR⁵(L^(4s))- or -(L^(3s)) alternatively, -(L^(3s))NR⁵(L^(4s))or alternatively, -(L^(3s))PR⁵(L^(4s))-. In an embodiment, the eachamin-di-yl group can have the formula —N(R⁵)—. In an embodiment, eachphosphin-di-yl group can have the formula —P(R⁵)—. In these L^(1s) groupformulas, the dashes represent the undesignated valance to which theX^(1s) and X^(2s) of the heteroatomic ligand described herein or theheteroatomic ligand of the heteroatomic ligand of the heteroatomicligand chromium compound complex described herein attach. In somenon-limiting embodiments, the heteroatomic ligand can have StructurePNP1, Structure PNP2, Structure NRN, Structure PRP, Structure SRN,Structure PRN, and Structure NRP; alternatively, Structure PNP1 orStructure PNP2; alternatively, Structure PRP, Structure SRN, orStructure PRN; alternatively, Structure PNP 1; alternatively, StructurePNP2; alternatively, Structure NRN; alternatively, Structure PRP;alternatively, Structure SRN; alternatively, Structure PRN; oralternatively, Structure NRP. In some non-limiting embodiments, theheteroatomic ligand chromium compound complex having a heteroatomicligand (R^(1s))_(m)X^(1s)(L^(1s))X^(1s))R^(1s))_(n) which can beutilized in catalyst systems described herein can have Structure PNCr1,Structure PNPCr2, Structure NRNCr, Structure PRPCr, Structure SRNCr,Structure PRNCr, and Structure NRPCr; alternatively, Structure PNPCr1 orStructure PNPCr2; alternatively, Structure PRPCr, Structure SRNCr, orStructure PRNCr; alternatively, Structure PNPCr1; alternatively,Structure PNPCr2; alternatively, Structure NRNCr; alternatively,Structure PRPCr; alternatively, Structure SRNCr; alternatively,Structure PRNCr; or alternatively, Structure NRPCr.

R^(5s), L^(2s), L^(3s), L^(4s), R^(11s), R^(12s), R^(13s), and R^(14s)are each independent elements of any of the organylene groups describedherein, any of the amin-di-yl groups described herein, any of thephosphin-di-yl groups described herein, any of the heteroatomic ligandshaving Structure PNP1, Structure PNP2, Structure NRN, Structure PRP,Structure SRN, Structure PRN, and Structure NRP, and any heteroatomicligand portion of the heteroatomic ligand chromium compound complexeshaving Structure PNCr1, Structure PNPCr2, Structure NRNCr, StructurePRPCr, Structure SRNCr, Structure PRNCr, and Structure NRPCr in whichthey occur and are independently described herein. The independentdescriptions of R^(5s), L^(2s), L^(3s), L^(4s), R^(11s), R^(12s),R^(13s), and R^(14s) can be utilized without limitation, and in anycombination, to further describe any of the organylene groups describedherein, any of the amin-di-yl groups described herein, any of thephosphin-di-yl groups described herein, any heteroatomic ligandstructure provided herein, and/or any heteroatomic ligand chromiumcompound complex structure provided herein in which they occur.Similarly, CrX_(p) is an independent element of the heteroatomic ligandchromium compound complexes having Structure PNCr1, Structure PNPCr2,Structure NRNCr, Structure PRPCr, Structure SRNCr, Structure PRNCr, andStructure NRPCr and is independently described herein. The independentdescription of CrX_(p) can be utilized without limitation, and in anycombination, to further describe the chromium compound portion of anyheteroatomic ligand chromium compound complex described herein and/orany heteroatomic ligand chromium compound complex structure providedherein. Additionally, the independent description of CrX_(p) can beutilized without limitation, and in any combination, with theindependently described R^(5s), L^(2s), L^(3s), L^(4s), R^(11s),R^(12s), R^(13s), and R^(14s) provided herein to further describe anyheteroatomic ligand chromium compound complex structure provided herein.

Generally, each R^(1s), R^(2s), R^(11s), R^(12s), R^(13s), and R^(14s)of any heteroatomic ligand described herein, any heteroatomic ligand ofthe heteroatomic ligand chromium compound complex described herein, anyheteroatomic ligand formula or structure provided herein, and/or anyheteroatomic ligand chromium compound complex structure provided hereinhaving a R^(1s), R^(2s), R^(11s), R^(12s), R^(13s), and/or R^(14s)and/or independently can be an organyl group; alternatively, an organylgroup consisting of inert functional groups; or alternatively, ahydrocarbyl group. In an embodiment, the organyl group which can beutilized as R^(1s), R^(2s), R^(11s), R^(12s), R^(13s), and R^(14s) canbe a C₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or a C₁ to C₅ organyl group.In an embodiment, the organyl group consisting of inert functionalgroups which can be utilized as R^(1s), R^(2s), R^(11s), R^(12s),R^(13s), and/or R^(14s) can be a C₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, ora C₁ to C₅ organyl group consisting of inert functional groups. In anembodiment, the hydrocarbyl group which can be utilized as R^(1s),R^(2s), R^(11s), R^(12s), R^(13s), and/or R^(14s) can be a C₁ to C₂₀, aC₁ to C₁₅, a C₁ to C₁₀, or a C₁ to C₅ hydrocarbyl group. In furtherembodiments, R^(1s) and R^(2s), R^(11s) and R^(12s), and/or R^(13s) andR^(14s) can be joined to form a ring or a ring system.

In an embodiment, each R^(1s), R^(2s), R^(11s), R^(12s), R^(13s), andR^(14s) of any heteroatomic ligand described herein, any heteroatomicligand of the heteroatomic ligand chromium compound complex describedherein, any heteroatomic ligand formula or structure provided herein,and/or any heteroatomic ligand chromium compound complex structureprovided herein having a R^(1s), R^(2s), R^(11s), R^(12s), R^(13s),and/or R^(14s) independently can be independently can be an alkyl group,a substituted alkyl group, a cycloalkyl group, a substituted cycloalkylgroup, an aryl group, a substituted aryl group, an aralkyl group, or asubstituted aralkyl group; alternatively, an alkyl group or asubstituted alkyl group; alternatively, a cycloalkyl group or asubstituted cycloalkyl group; alternatively, an aryl group or asubstituted aryl group; alternatively, an aralkyl group or a substitutedaralkyl group; or alternatively, an alkyl group, a cycloalkyl group, anaryl group, or an aralkyl group. In other embodiments, each R^(1s),R^(2s), R^(11s), R^(12s), R^(13s), and R^(14s) of any heteroatomicligand described herein, any heteroatomic ligand of the heteroatomicligand chromium compound complex described herein, any heteroatomicligand formula or structure provided herein, and/or any heteroatomicligand chromium compound complex structure provided herein having aR^(1s), R^(2s), R^(11s), R^(12s), R^(13s), and R^(14s) independently canbe an alkyl group; alternatively, a substituted alkyl roup,alternatively, a cycloalkyl group; alternatively, a substitutedcycloalkyl group; alternatively, an aryl group; alternatively, asubstituted aryl group; alternatively, an aralkyl group; oralternatively, a substituted aralkyl group.

In any aspect or embodiment disclosed herein, each alkyl group which canbe utilized as R^(1s), R^(2s), R^(11s), R^(12s), R^(13s), and/or R^(14s)independently can be a C₁ to C₂₀, a C₁ to C₁₀, or a C₁ to C₅ alkylgroup. In any aspect or embodiment disclosed herein, each substitutedalkyl group which can be utilized as R^(1s), R^(2s), R^(11s), R^(12s),R^(13s), and/or R^(14s) independently can be a C₁ to C₂₀, a C₁ to C₁₀,or a C₁ to C₅ substituted alkyl group. In any aspect or embodimentdisclosed herein, each cycloalkyl group which can be utilized as R^(1s),R^(2s), R^(11s), R^(12s), R^(13s), and/or R^(14s) independently can be aC₄ to C₂₀, a C₄ to C₁₅, or a C₄ to C₁₀ cycloalkyl group. In any aspector embodiment disclosed herein, each substituted cycloalkyl group whichcan be utilized as R^(1s), R^(2s), R^(11s), R^(12s), R^(13s), and/orR^(14s) independently can be a C₄ to C₂₀, a C₄ to C₁₅, or a C₄ to C₁₀substituted cycloalkyl group. In any aspect or embodiment disclosedherein, each aryl group which can be utilized as R^(1s), R^(2s),R^(11s), R^(12s), R^(13s), and/or R^(14s) independently can be a C₆ toC₂₀, a C₆ to C₁₅, or a C₆ to C₁₀ aryl group. In any aspect or embodimentdisclosed herein, each substituted aryl group which can be utilized asR^(1s), R^(2s), R^(11s), R^(12s), R^(13s), and/or R^(14s) independentlycan be a C₆ to C₂₀, a C₆ to C₁₅, or a C₆ to C₁₀ substituted aryl group.In any aspect or embodiment disclosed herein, each aralkyl group whichcan be utilized as R^(1s), R^(2s), R^(11s), R^(12s), R^(13s), and/orR^(14s) independently can be a C₇ to C₂₀, a C₇ to C₁₅, or a C₇ to C₁₀aralkyl group. In any aspect or embodiment disclosed herein, eachsubstituted aryl group which can be utilized as R^(1s), R^(2s), R^(11s),R^(12s), R^(13s), and/or R^(14s) independently can be a C₇ to C₂₀, a C₇to C₁₅, or a C₇ to C₁₀ substituted aralkyl group. Each substituent of asubstituted alkyl group (general or specific), a substituted cycloalkylgroup (general or specific), a substituted aryl group (general orspecific), and/or substituted aralkyl group (general or specific) can bea halogen, a hydrocarbyl group, or a hydrocarboxy group; alternatively,a halogen or a hydrocarbyl group; alternatively, a halogen or ahydrocarboxy group; alternatively, a hydrocarbyl group or a hydrocarboxygroup; alternatively, a halogen; alternatively, a hydrocarbyl group; oralternatively, a hydrocarboxy group. Substituent halogens, substituenthydrocarbyl groups (general and specific), and substituent hydrocarboxygroups (general and specific) are independently disclosed herein. Thesesubstituent halogens, substituent hydrocarboxy groups, and substituenthydrocarboxy groups can be utilized without limitation to furtherdescribe a substituted group (general or specific) which can be utilizedR^(1s), R^(2s), R^(11s), R^(12s), R^(13s), and/or R^(14s).

In an embodiment, each R^(1s), R^(2s), R^(11s), R^(12s), R^(13s), andR^(14s), when present in any heteroatomic ligand described herein, anyheteroatomic ligand of the heteroatomic ligand chromium compound complexdescribed herein, any heteroatomic ligand formula or structure providedherein, and/or any heteroatomic ligand chromium compound complexstructure provided herein, independently can be a methyl group, an ethylgroup, a propyl group, a butyl group, a pentyl group, a hexyl group, aheptyl group, or an octyl group; alternatively, a methyl group, an ethylgroup, an iso-propyl (2-propyl) group, a tert-butyl (2-methyl-2-propyl)group, or a neopentyl (2,2-dimethyl-1-propyl) group; alternatively, amethyl group; alternatively, an ethyl group; alternatively, a n-propyl(1-propyl) group; alternatively, an iso-propyl (2-propyl) group;alternatively, a tert-butyl (2-methyl-2-propyl) group; or alternatively,a neopentyl (2,2-dimethyl-1-propyl) group. In some embodiments, thealkyl groups which can be utilized as each R^(1s), R^(2s), R^(11s),R^(12s), R^(13s), and R^(14s) independently can be substituted. Eachsubstituent of a substituted alkyl group independently can be a halogenor a hydrocarboxy group; alternatively, a halogen; or alternatively, ahydrocarboxy group. Substituent halogens and substituent hydrocarboxygroups (general and specific) are independently disclosed herein. Thesesubstituent halogens and substituent hydrocarboxy groups can be utilizedwithout limitation to further describe a substituted alkyl group(general or specific) which can be utilized as R^(1s), R^(2s), R^(11s),R^(12s), R^(13s), and/or R^(14s).

In an embodiment, each R^(1s), R^(2s), R^(11s), R^(12s), R^(13s), andR^(14s), when present in any heteroatomic ligand described herein, anyheteroatomic ligand of the heteroatomic ligand chromium compound complexdescribed herein, any heteroatomic ligand formula or structure providedherein, and/or any heteroatomic ligand chromium compound complexstructure provided herein, independently can be a cyclopentyl group, asubstituted cyclopentyl group, a cyclohexyl group, or a substitutedcyclohexyl group; alternatively, a cyclopentyl group or a substitutedcyclopentyl group; or alternatively, a cyclohexyl group or a substitutedcyclohexyl group; alternatively, a cyclopentyl group; alternatively, asubstituted cyclopentyl group; alternatively, a cyclohexyl group; oralternatively, a substituted cyclohexyl group. In an embodiment, thesubstituted cycloalkyl group, which can be utilized for any of R^(1s),R^(2s), R^(11s), R^(12s), R^(13s), and/or R^(14s), when present in anyheteroatomic ligand described herein, any heteroatomic ligand of theheteroatomic ligand chromium compound complex described herein, anyheteroatomic ligand formula or structure provided herein, and/or anyheteroatomic ligand chromium compound complex structure provided herein,independently can be a 2-substituted cyclohexyl group, a2,6-disubstituted cyclohexyl group, a 2-substituted cyclopentyl group,or a 2,6-disubstituted cyclopentyl group; alternatively, a 2-substitutedcyclohexyl group or a 2,6-disubstituted cyclohexyl group; alternatively,a 2-substituted cyclopentyl group or a 2,6-disubstituted cyclopentylgroup; alternatively, a 2-substituted cyclohexyl group or a2-substituted cyclopentyl group; alternatively, a 2,6-disubstitutedcyclohexyl group or a 2,6-disubstituted cyclopentyl group;alternatively, a 2-substituted cyclohexyl group; alternatively, a2,6-disubstituted cyclohexyl group; alternatively, a 2-substitutedcyclopentyl group; or alternatively, a 2,6-disubstituted cyclopentylgroup. In an embodiment, one or more substituents of a multi-substitutedcycloalkyl group utilized as R^(1s), R^(2s), R^(11s), R^(12s), R^(13s),and/or R^(14s) can be the same or different; alternatively, all thesubstituents of a multi-substituted cycloalkyl group can be the same; oralternatively, all the substituents of a multi-substituted cycloalkylgroup can be different. Each substituent of a substituted cycloalkylgroup (general or specific) having a specified number of ring carbonatoms independently can be a halogen, a hydrocarbyl group, or ahydrocarboxy group; alternatively, a halogen or a hydrocarbyl group;alternatively, a halogen or a hydrocarboxy group; alternatively, ahydrocarbyl group or a hydrocarboxy group; alternatively, a halogen,alternatively, a hydrocarbyl group; or alternatively, a hydrocarboxygroup. Substituent halogens, substituent hydrocarbyl groups (general andspecific), and substituent hydrocarboxy groups (general and specific)are independently disclosed herein. These substituent halogens,substituent hydrocarbyl groups, and substituent hydrocarboxy groups canbe utilized without limitation to further describe a substitutedcycloalkyl group (general or specific) which can be utilized as R^(1s),R^(2s), R^(11s), R^(12s), R^(13s), and/or R^(14s).

In a non-limiting embodiment, each R^(1s), R^(2s), R^(11s), R^(12s),R^(13s), and/or R^(14s), when present in any heteroatomic liganddescribed herein, any heteroatomic ligand of the heteroatomic ligandchromium compound complex described herein, any heteroatomic ligandformula or structure provided herein, and/or any heteroatomic ligandchromium compound complex structure provided herein, independently canbe a cyclohexyl group, a 2-alkylcyclohexyl group, or a2,6-dialkylcyclohexyl group; alternatively, a cyclopentyl group, a2-alkylcyclopentyl group, or a 2,5-dialkylcyclopentyl group;alternatively, a cyclohexyl group; alternatively, a 2-alkylcyclohexylgroup; alternatively, a 2,6-dialkylcyclohexyl group; alternatively, acyclopentyl group; alternatively, a 2-alkylcyclopentyl group; oralternatively, a 2,5-dialkylcyclopentyl group. Alkyl substituent groups(general and specific) are independently described herein and thesealkyl substituent groups can be utilized, without limitation, to furtherdescribe alkylcyclohexyl groups (general or specific), dialkylcyclohexylgroups (general or specific), alkylcyclopentyl groups (general orspecific), and/or dialkylcyclopentyl groups (general or specific) whichcan be utilized as R^(1s), R^(2s), R^(11s), R^(12s), R^(13s), and/orR^(14s). Generally, the alkyl substituents of a disubstituted cyclohexylor cyclopentyl group can be the same, or alternatively, the alkylsubstituents can be different. In some non-limiting embodiments, eachR^(1s), R^(2s), R^(11s), R^(12s), R^(13s), and/or R^(14s), when presentin any heteroatomic ligand described herein, any heteroatomic ligand ofthe heteroatomic ligand chromium compound complex described herein, anyheteroatomic ligand formula or structure provided herein, and/or anyheteroatomic ligand chromium compound complex structure provided herein,independently can be a 2-methylcyclohexyl group, a 2-ethylcyclohexylgroup, a 2-isopropylcyclohexyl group, a 2-tert-butylcyclohexyl group, a2,6-dimethylcyclohexyl group, a 2,6-diethylcyclohexyl group, a2,6-diisopropylcyclohexyl group, or a 2,6-di-tert-butylcyclohexyl group;alternatively, a 2-methylcyclohexyl group, a 2-ethylcyclohexyl group, a2-isopropylcyclohexyl group, or a 2-tert-butylcyclohexyl group; oralternatively, a 2,6-dimethylcyclohexyl group, a 2,6-diethylcyclohexylgroup, a 2,6-diisopropylcyclohexyl group, or a2,6-di-tert-butylcyclohexyl group.

In an embodiment, each R^(1s), R^(2s), R^(11s), R^(12s), R^(13s), andR^(14s), when present in any heteroatomic ligand described herein, anyheteroatomic ligand of the heteroatomic ligand chromium compound complexdescribed herein, any heteroatomic ligand formula or structure providedherein, and/or any heteroatomic ligand chromium compound complexstructure provided herein, independently can be a phenyl group or asubstituted phenyl group; alternatively, a phenyl group; oralternatively, a substituted phenyl group. In an embodiment, thesubstituted phenyl group which can be utilized for each R^(1s), R^(2s),R^(11s), R^(12s), R^(13s), and/or R^(14s), when present in anyheteroatomic ligand described herein, any heteroatomic ligand of theheteroatomic ligand chromium compound complex described herein, anyheteroatomic ligand formula or structure provided herein, and/or anyheteroatomic ligand chromium compound complex structure provided herein,independently can be a 2-substituted phenyl group, a 3-substitutedphenyl group, a 4-substituted phenyl group, a 2,4-disubstituted phenylgroup, a 2,6-disubstituted phenyl group, a 3,5-disubstituted phenylgroup, or a 2,4,6-trisubstituted phenyl group; alternatively, a2-substituted phenyl group, a 4-substituted phenyl group, a2,4-disubstituted phenyl group, or a 2,6-disubstituted phenyl group;alternatively, a 3-substituted phenyl group or a 3,5-disubstitutedphenyl group; alternatively, a 2-substituted phenyl group or a4-substituted phenyl group; alternatively, a 2,4-disubstituted phenylgroup or a 2,6-disubstituted phenyl group; alternatively, a2-substituted phenyl group; alternatively, a 3-substituted phenyl group;alternatively, a 4-substituted phenyl group; alternatively, a2,4-disubstituted phenyl group; alternatively, a 2,6-disubstitutedphenyl group; alternatively, a 3,5-disubstituted phenyl group; oralternatively, a 2,4,6-trisubstituted phenyl group. In an embodiment,one or more substituents of a multi-substituted phenyl group utilized asR^(1s), R^(2s), R^(11s), R^(12s), R^(13s), and/or R^(14s) can be thesame or different; alternatively, all the substituents can be the same;or alternatively, all the substituents can be different. Eachsubstituent of a substituted phenyl group (general or specific)independently can be a halogen, a hydrocarbyl group, or a hydrocarboxygroup; alternatively, a halogen or a hydrocarbyl group; alternatively, ahalogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or ahydrocarboxy group; alternatively, a halogen; alternatively, ahydrocarbyl group; or alternatively, a hydrocarboxy group. Substituenthalogens, substituent hydrocarbyl groups (general and specific), andsubstituent hydrocarboxy groups (general and specific) are independentlydisclosed herein. These substituent halogens, substituent hydrocarbylgroups, and substituent hydrocarboxy group can be utilized withoutlimitation to further describe a substituted phenyl group (general orspecific) which can be utilized as R^(1s), R^(2s), R^(11s), R^(12s),R^(13s), and/or R^(14s).

In a non-limiting embodiment, each R^(1s), R^(2s), R^(11s), R^(12s),R^(13s), and R^(14s), when present in any heteroatomic ligand describedherein, any heteroatomic ligand of the heteroatomic ligand chromiumcompound complex described herein, any heteroatomic ligand formula orstructure provided herein, and/or any heteroatomic ligand chromiumcompound complex structure provided herein, independently can be aphenyl group, a 2-alkylphenyl group, a 3-alkylphenyl group, a4-alkylphenyl group, a 2,4-dialkylphenyl group, a 2,6-dialkylphenylgroup, a 3,5-dialkylphenyl group, or a 2,4,6-trialkylphenyl group;alternatively, a 2-alkylphenyl group, a 4-alkylphenyl group, a2,4-dialkylphenyl group, a 2,6-dialkylphenyl group, or a2,4,6-trialkylphenyl group; alternatively, a 2-alkylphenyl group or a4-alkylphenyl group; alternatively, a 2,4-dialkylphenyl group or a2,6-dialkylphenyl group; alternatively, a 3-alkylphenyl group or a3,5-dialkylphenyl group; alternatively, a 2-alkylphenyl group or a2,6-dialkylphenyl group; alternatively, a 2-alkylphenyl group;alternatively, a 4-alkylphenyl group; alternatively, a 2,4-dialkylphenylgroup; alternatively, a 2,6-dialkylphenyl group; or alternatively, a2,4,6-trialkylphenyl group. Alkyl substituent groups (general andspecific) are independently described herein and these alkyl substituentgroups can be utilized, without limitation, to further describe anyalkyl substituted phenyl group which can be utilized as R^(1s), R^(2s),R^(11s), R^(12s), R^(13s), and/or R^(14s). Generally, the alkylsubstituents of dialkylphenyl groups (general or specific) ortrialkylphenyl groups (general or specific) can be the same, oralternatively, the alkyl substituents can be different. In somenon-limiting embodiments, each R^(1s), R^(2s), R^(11s), R^(12s),R^(13s), and R^(14s), when present in any heteroatomic ligand describedherein, any heteroatomic ligand of the heteroatomic ligand chromiumcompound complex described herein, any heteroatomic ligand formula orstructure provided herein, and/or any heteroatomic ligand chromiumcompound complex structure provided herein, independently can be aphenyl group, a 2-methylphenyl group, a 2-ethylphenyl group, a2-n-propylphenyl group, a 2-isopropylphenyl group, a 2-tert-butylphenylgroup, a 2,6-dimethylphenyl group, a 2,6-diethylphenyl group, a2,6-di-n-propylphenyl group, a 2,6-diisopropylphenyl group, a2,6-di-tert-butylphenyl group, a 2-isopropyl-6-methylphenyl group, or a2,4,6-trimethylphenyl group; alternatively, a phenyl group, a2-methylphenyl group, a 2-ethylphenyl group, a 2-n-propylphenyl group, a2-isopropylphenyl group, or a 2-tert-butylphenyl group; oralternatively, a phenyl group, a 2,6-dimethylphenyl group, a2,6-diethylphenyl group, a 2,6-di-n-propylphenyl group, a2,6-diisopropylphenyl group, a 2,6-di-tert-butylphenyl group, a2-isopropyl-6-methylphenyl group, or a 2,4,6-trimethylphenyl group.

In a non-limiting embodiment, each R^(1s), R^(2s), R^(11s), R^(12s),R^(13s), and R^(14s), when present in any heteroatomic ligand describedherein, any heteroatomic ligand of the heteroatomic ligand chromiumcompound complex described herein, any heteroatomic ligand formula orstructure provided herein, and/or any heteroatomic ligand chromiumcompound complex structure provided herein, independently can be aphenyl group, a 2-alkoxyphenyl group, or a 4-alkoxyphenyl group. In somenon-limiting embodiments, each R^(1s), R^(2s), R^(11s), R^(12s),R^(13s), and R^(14s), when present in any heteroatomic ligand describedherein, any heteroatomic ligand of the heteroatomic ligand chromiumcompound complex described herein, any heteroatomic ligand formula orstructure provided herein, and/or any heteroatomic ligand chromiumcompound complex structure provided herein, independently can be aphenyl group, a 2-methoxyphenyl group, a 2-ethoxyphenyl group, a2-isopropoxyphenyl group, a 2-tert-butoxyphenyl group, a 4-methoxyphenylgroup, a 4-ethoxyphenyl group, a 4-isopropoxyphenyl group, or a4-tert-butoxyphenyl group; alternatively, a 2-methoxyphenyl group, a2-ethoxyphenyl group, a 2-isopropoxyphenyl group, or a2-tert-butoxyphenyl group; or alternatively, a 4-methoxyphenyl group, a4-ethoxyphenyl group, a 4-isopropoxyphenyl group, or a4-tert-butoxyphenyl group.

In a non-limiting embodiment, each R^(1s), R^(2s), R^(11s), R^(12s),R^(13s), and R^(14s), when present in any heteroatomic ligand describedherein, any heteroatomic ligand of the heteroatomic ligand chromiumcompound complex described herein, any heteroatomic ligand formula orstructure provided herein, and/or any heteroatomic ligand chromiumcompound complex structure provided herein, independently can be aphenyl group, a 2-halophenyl group, a 4-halophenyl group, or a2,6-dihalophenylgroup. Generally, the halides of a dihalophenyl groupcan be the same, or alternatively, the halides can be different. In someembodiments, each R^(1s), R^(2s), R^(11s), R^(12s), R^(13s), andR^(14s), when present in any heteroatomic ligand described herein, anyheteroatomic ligand of the heteroatomic ligand chromium compound complexdescribed herein, any heteroatomic ligand formula or structure providedherein, and/or any heteroatomic ligand chromium compound complexstructure provided herein, independently can be a phenyl group, a2-fluorophenyl group, a 4-fluorophenyl group, or a 2,6-difluorophenylgroup.

In an embodiment, each R^(1s), R^(2s), R^(11s), R^(12s), R^(13s), andR^(14s), when present in any heteroatomic ligand described herein, anyheteroatomic ligand of the heteroatomic ligand chromium compound complexdescribed herein, any heteroatomic ligand formula or structure providedherein, and/or any heteroatomic ligand chromium compound complexstructure provided herein, independently can be a benzyl group or asubstituted benzyl group; alternatively, a benzyl group; oralternatively, a substituted benzyl group. Each substituent of asubstituted benzyl group (general or specific) independently can be ahalogen, a hydrocarbyl group, or a hydrocarboxy group; alternatively, ahalogen or a hydrocarbyl group; alternatively, a halogen or ahydrocarboxy group; alternatively, a hydrocarbyl group or a hydrocarboxygroup; alternatively, a halogen, alternatively, a hydrocarbyl group; oralternatively, a hydrocarboxy group. Substituent halogens, substituenthydrocarbyl groups (general and specific), and substituent hydrocarboxygroups (general and specific) are independently disclosed herein. Thesesubstituent halogens, substituent hydrocarbyl groups, and substituenthydrocarboxy groups can be utilized without limitation to furtherdescribe a substituted benzyl group (general or specific) which can beutilized as R^(1s), R^(2s), R^(11s), R^(12s), R^(13s), and/or R^(14s).

Generally, R^(5s) of any organylene L^(1s) group disclosed herein, anyamin-di-yl group disclosed herein, any phosphin-di-yl group disclosedherein, any heteroatomic ligand structure provided herein, and/or anyheteroatomic ligand chromium compound complex structure provided hereincan be an organyl group; alternatively, an organyl group consisting ofinert functional groups; or alternatively, a hydrocarbyl group. In anembodiment, the organyl group which can be utilized as R^(5s) can be aC₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or a C₁ to C₅ organyl group. In anembodiment, the organyl group consisting of inert functional groupswhich can be utilized as R^(5s) can be a C₁ to C₂₀, a C₁ to C₁₅, a C₁ toC₁₀, or a C₁ to C₅ organyl group consisting of inert functional groups.In an embodiment, the hydrocarbyl group which can be utilized as R^(5s)can be a C₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or a C₁ to C₅ hydrocarbylgroup.

In an embodiment, R^(5s) of any organylene L^(1s) group disclosedherein, any amin-di-yl group disclosed herein, any phosphin-di-yl groupdisclosed herein, any heteroatomic ligand structure provided herein,and/or any heteroatomic ligand chromium compound complex structureprovided herein can be an alkyl group, a substituted alkyl group, acycloalkyl group, a substituted cycloalkyl group, an aryl group, asubstituted aryl group, an aralkyl group, or a substituted aralkylgroup. In some embodiments, R^(5s) of any organylene L^(1s) groupdisclosed herein, any amin-di-yl group disclosed herein, anyphosphin-di-yl group disclosed herein, any heteroatomic ligand structureprovided herein, and/or any heteroatomic ligand chromium compoundcomplex structure provided herein can be an alkyl group or a substitutedalkyl group; alternatively, a cycloalkyl group or a substitutedcycloalkyl group; alternatively, an aryl group or a substituted arylgroup; alternatively, an aralkyl group or a substituted aralkyl group;or alternatively, an alkyl group, a cycloalkyl group, an aryl group, oran aralkyl group. In other embodiments, R^(5s) of any organylene L^(1s)group disclosed herein, any amin-di-yl group disclosed herein, anyphosphin-di-yl group disclosed herein, any heteroatomic ligand structureprovided herein, and/or any heteroatomic ligand chromium compoundcomplex structure provided herein can be an alkyl group; alternatively,a substituted alkyl group, alternatively, a cycloalkyl group;alternatively, a substituted cycloalkyl group; alternatively, an arylgroup; alternatively, a substituted aryl group; alternatively, anaralkyl group; or alternatively, a substituted aralkyl group.

In any aspect or embodiment disclosed herein, the alkyl group which canbe utilized as R^(5s) can be a C₁ to C₂₀, a C₁ to C₁₅, or a C₁ to C₁₀alkyl group. In any aspect or embodiment disclosed herein, thesubstituted alkyl group which can be utilized as R^(5s) can be a C₁ toC₂₀, a C₁ to C₁₅, or a C₁ to C₁₀ substituted alkyl group. In any aspector embodiment disclosed herein, the cycloalkyl group which can beutilized as R^(5s) can be a C₄ to C₂₀, a C₄ to C₁₅, or a C₄ to C₁₀cycloalkyl group. In any aspect or embodiment disclosed herein, thesubstituted cycloalkyl group which can be utilized as R^(5s) can be a C₄to C₂₀, a C₄ to, or a C₄ to C₁₀ substituted cycloalkyl group. In anyaspect or embodiment disclosed herein, the aryl group which can beutilized as R^(5s) can be a C₆ to C₂₀, a C₆ to C₁₅, or a C₆ to C₁₀ arylgroup. In any aspect or embodiment disclosed herein, the substitutedaryl group which can be utilized as R^(5s) can be a C₆ to C₂₀, a C₆ toC₁₅, or a C₆ to C₁₀ substituted aryl group. In any aspect or embodimentdisclosed herein, each aralkyl group which can be utilized as R^(5s) canbe a C₇ to C₂₀, a C₇ to C₁₅, or a C₇ to C₁₀ aralkyl group. In any aspector embodiment disclosed herein, the substituted aryl group which can beutilized as R^(5s) can be a C₇ to C₂₀, a C₇ to C₁₅, or a C₇ to C₁₀substituted aralkyl group. Each substituent of a substituted alkyl group(general or specific), substituted cycloalkyl group (general orspecific), substituted aryl group (general or specific), and/orsubstituted aralkyl group (general or specific) can be a halogen,hydrocarbyl group, or a hydrocarboxy group; alternatively, a halogen ora hydrocarbyl group; alternatively, a halogen or a hydrocarboxyl group;alternatively, a hydrocarbyl group or a hydrocarboxy group;alternatively, a halogen; alternatively, a hydrocarbyl group; oralternatively, a hydrocarboxy group. Substituent halogens, hydrocarbylgroups (general and specific), and substituent hydrocarboxy groups(general and specific) are independently disclosed herein. Thesesubstituent halogens, substituent hydrocarbyl groups, and substituenthydrocarboxy groups can be utilized without limitation to furtherdescribe a substituted group (general or specific) which can be utilizedR^(5s).

In an embodiment, R^(5s) of any organylene L^(1s) group disclosedherein, any amin-di-yl group disclosed herein, any phosphin-di-yl groupdisclosed herein, any heteroatomic ligand structure provided herein,and/or any heteroatomic ligand chromium compound complex structureprovided herein can be a methyl group, an ethyl group, a propyl group, abutyl group, a pentyl group, a hexyl group, a heptyl group, or an octylgroup; alternatively, a methyl group, an ethyl group, an n-propyl(1-propyl) group, an isopropyl (2-propyl) group, an n-butyl (1-butyl)group, a sec-butyl (2-butyl) group, an isobutyl (2-methyl-1-propyl)group, a tert-butyl (2-methyl-2-propyl) group, an n-pentyl (1-pentyl)group, a 2-pentyl group, a 3-pentyl group, a 2-methyl-1-butyl group, atert-pentyl (2-methyl-2-butyl) group, a 3-methyl-1-butyl group, a3-methyl-2-butyl group, or a neo-pentyl (2,2-dimethyl-1-propyl) group;alternatively, a methyl group, an ethyl group, an iso-propyl (2-propyl)group, a tert-butyl (2-methyl-2-propyl) group, or a neopentyl(2,2-dimethyl-1-propyl) group; alternatively, a methyl group;alternatively, an ethyl group; alternatively, a n-propyl (1-propyl)group; alternatively, an iso-propyl (2-propyl) group; alternatively, atert-butyl (2-methyl-2-propyl) group; or alternatively, a neopentyl(2,2-dimethyl-1-propyl) group. In some embodiments, the alkyl groupswhich can be utilized as R^(5s) can be substituted. Each substituent ofa substituted alkyl group independently can be a halogen or ahydrocarboxy group; alternatively, a halogen; or alternatively, ahydrocarboxy group. Substituent halogens and substituent hydrocarboxygroups (general and specific) are independently described herein andthese substituent groups can be utilized without limitation to furtherdescribe a substituted alkyl group (general or specific) which can beutilized as R^(5s).

In an embodiment, R^(5s) of any organylene L^(1s) group disclosedherein, any amin-di-yl group disclosed herein, any phosphin-di-yl groupdisclosed herein, any heteroatomic ligand structure provided herein,and/or any heteroatomic ligand chromium compound complex structureprovided herein can be a cyclopentyl group, a substituted cyclopentylgroup, a cyclohexyl group, a substituted cyclohexyl group;alternatively, a cyclopentyl group or a substituted cyclopentyl group;alternatively, a cyclohexyl group or a substituted cyclohexyl group;alternatively, a cyclopentyl group; alternatively, a substitutedcyclopentyl group; alternatively, a cyclohexyl group; or alternatively,a substituted cyclohexyl group. In further embodiments, R^(5s) of anyorganylene L^(1s) group disclosed herein, any amin-di-yl group disclosedherein, any phosphin-di-yl group disclosed herein, any heteroatomicligand structure provided herein, and/or any heteroatomic ligandchromium compound complex structure provided herein can be a2-substituted cyclohexyl group, a 2,6-disubstituted cyclohexyl group, a2-substituted cyclopentyl group, or a 2,6-disubstituted cyclopentylgroup; alternatively, a 2-substituted cyclohexyl group or a2,6-disubstituted cyclohexyl group; alternatively, a 2-substitutedcyclohexyl group or a 2,6-disubstituted cyclohexyl group; alternatively,a 2-substituted cyclopentyl group or a 2,6-disubstituted cyclopentylgroup; alternatively, a 2-substituted cyclohexyl group or a2-substituted cyclopentyl group; alternatively, a 2,6-disubstitutedcyclohexyl group or a 2,6-disubstituted cyclopentyl group;alternatively, a 2-substituted cyclohexyl group; alternatively, a2,6-disubstituted cyclohexyl group; alternatively, a 2-substitutedcyclopentyl group; or alternatively, a 2,6-disubstituted cyclopentylgroup. In an embodiment, one or more substituents of a multi-substitutedcycloalkyl group utilized as R^(5s) can be the same or different;alternatively, all the substituents of a multi-substituted cycloalkylgroup can be the same; or alternatively, all the substituents of amulti-substituted cycloalkyl group can be different. Each substituent ofa cycloalkyl group (general or specific) having a specified number ofring carbon atoms independently can be a halogen, a hydrocarbyl group,or a hydrocarboxy group; alternatively, a halogen or a hydrocarbylgroup; alternatively, a halogen or a hydrocarboxy group; alternatively,a hydrocarbyl group or a hydrocarboxy group; alternatively, a halogen;alternatively, a hydrocarbyl group; or alternatively, a hydrocarboxygroup. Substituent halogens, substituent hydrocarbyl groups (general andspecific), and substituent hydrocarboxy groups (general and specific)are independently described herein and these substituent groups can beutilized without limitation to further describe a substituted cycloalkylgroup (general or specific) which can be utilized as R^(5s).

In a non-limiting embodiment, R^(5s) of any organylene L^(1s) groupdisclosed herein, any amin-di-yl group disclosed herein, anyphosphin-di-yl group disclosed herein, any heteroatomic ligand structureprovided herein, and/or any heteroatomic ligand chromium compoundcomplex structure provided herein can be a cyclohexyl group, a2-alkylcyclohexyl group, or a 2,6-dialkylcyclohexyl group;alternatively, a cyclopentyl group, a 2-alkylcyclopentyl group, or a2,5-dialkylcyclopentyl group; alternatively, a cyclohexyl group;alternatively, a 2-alkylcyclohexyl group; alternatively, a2,6-dialkylcyclohexyl group; alternatively, a cyclopentyl group;alternatively, a 2-alkylcyclopentyl group; or alternatively, a2,5-dialkylcyclopentyl group. Alkyl substituent groups (general andspecific) are independently described herein and these alkyl substituentgroups can be utilized, without limitation, to further describealkylcyclohexyl groups (general or specific), dialkylcyclohexyl groups(general or specific), alkylcyclopentyl groups (general or specific),and/or dialkylcyclopentyl groups (general or specific) which can beutilized as R⁵′. Generally, the alkyl substituents of a disubstitutedcyclohexyl or cyclopentyl group can be the same, or alternatively, thealkyl substituents can be different. In some non-limiting embodiments,R^(5s) heteroatomic ligand structure provided herein, and/or anyheteroatomic ligand chromium compound complex structure provided hereincan be a 2-methylcyclohexyl group, a 2-ethylcyclohexyl group, a2-isopropylcyclohexyl group, a 2-tert-butylcyclohexyl group, a2,6-dimethylcyclohexyl group, a 2,6-diethylcyclohexyl group, a2,6-diisopropylcyclohexyl group, or a 2,6-di-tert-butylcyclohexyl group.In other non-limiting embodiments, R^(5s) can be a 2-methylcyclohexylgroup, a 2-ethylcyclohexyl group, a 2-isopropylcyclohexyl group, or a2-tert-butylcyclohexyl group; or alternatively, a 2,6-dimethylcyclohexylgroup, a 2,6-diethylcyclohexyl group, a 2,6-diisopropylcyclohexyl group,or a 2,6-di-tert-butylcyclohexyl group. In an embodiment, R^(5s)heteroatomic ligand structure provided herein, and/or any heteroatomicligand chromium compound complex structure provided herein can be acyclopentyl group, a 2-methylcyclopentyl group, a cyclohexyl group, or a2-methylcyclohexyl group; alternatively, a cyclopentyl group or acyclohexyl group; or alternatively, a 2-methylcyclopentyl group or a2-methylcyclohexyl group.

In an embodiment, R^(5s) of any organylene L^(1s) group disclosedherein, any amin-di-yl group disclosed herein, any phosphin-di-yl groupdisclosed herein, any heteroatomic ligand structure provided herein,and/or any heteroatomic ligand chromium compound complex structureprovided herein can be a phenyl group or a substituted phenyl group;alternatively, a phenyl group; or alternatively, a substituted phenylgroup. In some embodiments, R^(5s) of any organylene L^(1s) groupdisclosed herein, any amin-di-yl group disclosed herein, anyphosphin-di-yl group disclosed herein, any heteroatomic ligand structureprovided herein, and/or any heteroatomic ligand chromium compoundcomplex structure provided herein can be a 2-substituted phenyl group, a4-substituted phenyl group, a 2,4-disubstituted phenyl group, a2,6-disubstituted phenyl group, or a 2,4,6-trisubstituted phenyl group;alternatively, a 2-substituted phenyl group or a 4-substituted phenylgroup; alternatively, a 2,4-disubstituted phenyl group, a2,6-disubstituted phenyl group, or a 2,4,6-trisubstituted phenyl group;alternatively, a 2,4-disubstituted phenyl group or a 2,6-disubstitutedphenyl group; alternatively, a 2-substituted phenyl group;alternatively, a 4-substituted phenyl group; alternatively, a2,4-disubstituted phenyl group; alternatively, a 2,6-disubstitutedphenyl group; or alternatively, a 2,4,6-trisubstituted phenyl group. Inan embodiment, one or more substituents of a multi-substituted phenylgroup utilized as R^(5s) can be the same or different; alternatively,all the substituents can be the same, or alternatively, all thesubstituents can be different. Each substituent of a substituted phenylgroup (general or specific) independently can be a halogen, ahydrocarbyl group, or a hydrocarboxy group; alternatively, a halogen ora hydrocarbyl group; alternatively, a halogen or a hydrocarboxy group;alternatively, a hydrocarbyl group or a hydrocarboxy group;alternatively, a halogen; alternatively, a hydrocarbyl group; oralternatively, a hydrocarboxy group. Substituent halogens, substituenthydrocarbyl groups (general and specific), and substituent hydrocarboxygroups (general and specific) are independently described herein andthese substituent groups can be utilized without limitation to furtherdescribe a substituted phenyl group (general or specific) which can beutilized as less.

In a non-limiting embodiment, R^(5s) of any organylene L^(1s) groupdisclosed herein, any amin-di-yl group disclosed herein, anyphosphin-di-yl group disclosed herein, any heteroatomic ligand structureprovided herein, and/or any heteroatomic ligand chromium compoundcomplex structure provided herein can be a phenyl group, a 2-alkylphenylgroup, a 4-alkylphenyl group, a 2,4-dialkylphenyl group, a2,6-dialkylphenyl group, or a 2,4,6-trialkylphenyl group; alternatively,a 2-alkylphenyl group, a 2,4-dialkylphenyl group, a 2,6-dialkylphenylgroup, or a 2,4,6-trialkylphenyl group. Alkyl substituent groups(general and specific) are independently described herein and thesealkyl substituent groups can be utilized, without limitation, to furtherdescribe any alkyl substituted phenyl group which can be utilized asR^(5s). Generally, the alkyl substituents of dialkylphenyl groups(general of specific) or trialkylphenyl groups (general or specific) canbe the same, or alternatively, the alkyl substituents can be different.In some non-limiting embodiments, R^(5s) of any organylene L^(1s) groupdisclosed herein, any amin-di-yl group disclosed herein, anyphosphin-di-yl group disclosed herein, any heteroatomic ligand structureprovided herein, and/or any heteroatomic ligand chromium compoundcomplex structure provided herein can be a phenyl group, a2-methylphenyl group, a 2-ethylphenyl group, a 2-n-propylphenyl group, a2-isopropylphenyl group, a 2-tert-butylphenyl group, a2,6-dimethylphenyl group, a 2,6-diethylphenyl group, a2,6-di-n-propylphenyl group, a 2,6-diisopropylphenyl group, a2,6-di-tert-butylphenyl group, a 2-isopropyl-6-methylphenyl group, or a2,4,6-trimethylphenyl group; alternatively, a phenyl group, a2-methylphenyl group, a 2,6-dimethylphenyl group, or a2,4,6-trimethylphenyl group.

Generally, L^(2s) of the heteroatomic ligand having Structure PNP2and/or the heteroatomic ligand chromium compound complex havingStructure PNPCr2 can be an organylene group; alternatively, anorganylene group consisting of inert functional groups; oralternatively, a hydrocarbylene group. In an embodiment, the organylenegroup which can be utilized as L^(2s) can be a C₁ to C₂₀, a C₁ to C₁₅,or a C₁ to C₁₀ organylene group. In an embodiment, the organylene groupconsisting of inert functional groups which can be utilized as L^(2s)can be a C₁ to C₂₀, a C₁ to C₁₅, or a C₁ to C₁₀ organylene groupconsisting of inert functional groups. In an embodiment, thehydrocarbylene group which can be utilized as L^(2s) can be a C₁ to C₂₀,a C₁ to C₁₅, or a C₁ to C₁₀ hydrocarbylene group. In an embodiment,L^(1s) of the heteroatomic ligand having Structure PNP2 and/or theheteroatomic ligand chromium compound complex having Structure PNPCr2can be a C₁ to C₂₀, C₁ to C₁₅, or a C₁ to C₁₀ alkylene group.

In an embodiment, L^(2s) of the heteroatomic ligand having StructurePNP2 and/or the heteroatomic ligand chromium compound complex havingStructure PNPCr2 can be —(CR^(P)R^(P))_(m)— where each R^(P) and R^(P′)can independently be hydrogen, methyl, ethyl, propyl, isopropyl, orbutyl groups and m can be an integer from 1 to 12. In some embodiments,L^(2s) of the heteroatomic ligand having Structure PNP2 and/or theheteroatomic ligand chromium compound complex having Structure PNPCr2can be a methylene group (—CH₂—), an ethylene group (—CH₂CH₂—), apropylene group (—CH₂CH₂CH₂—), a —CH(CH₃)CH₂— group, —C(CH₃)₂— group, abutylene group (—CH₂CH₂CH₂—CH₂—), or a —CH₂CH(CH₃)—CH₂— group. In otherembodiments, L^(1s) of the heteroatomic ligand having Structure PNP2and/or the heteroatomic ligand chromium compound complex havingStructure PNPCr2 can be a methylene group (—CH₂—), an ethylene group(—CH₂CH₂—), or a —CH(CH₃)CH₂-group; alternatively, a methylenegroup(—CH₂—); alternatively, an ethylene group (—CH₂CH₂—);alternatively, a propylene group (—CH₂CH₂CH₂—); alternatively, a—CH(CH₃)CH₂— group; alternatively, a —C(CH₃)₂— group; or alternatively,a —CH₂CH(CH₃)—CH₂— group.

In an embodiment, L^(2s) of the heteroatomic ligand having StructurePNP2 and/or the heteroatomic ligand chromium compound complex havingStructure PNPCr2 can be 1,2-cyclohexylene, a substituted1,2-cyclohexylene, 1,3-cyclohexylene, a substituted 1,3-cyclohexylene,1,4-cyclohexylene, a substituted 1,4-cyclohexylene,3,3′-bicyclohexylene, a substituted 3,3′-bicyclohexylene,4,4′-bicyclohexylene, a substituted 4,4′-bicyclohexylene,bis(3-cyclohexylene)methane, a substituted bis(3-cyclohexylene)methane,bis(4-cyclohexylene)methane, a substituted bis(4-cyclohexylene)methane,1,2-bis(3-cyclohexylene)ethane, a substituted1,2-bis(3-cyclohexylene)ethane, 1,2-bis(4-cyclohexylene)-ethane, asubstituted 1,2-bis(4-cyclohexylene)ethane,1,2-bis(3-cyclohexylene)propane, a substituted1,2-bis(3-cyclohexylene)propane, 1,2-bis(4-cyclohexylene)propane, asubstituted 1,2-bis(4-cyclohexylene)-propane,2,2-bis(3-cyclohexylene)propane, a substituted2,2-bis(3-cyclohexylene)propane, 2,2-bis(4-cyclohexylene)propane, or asubstituted 2,2-bis(4-cyclohexylene)propane. In some embodiments, L^(2s)of the heteroatomic ligand having Structure PNP2 and/or the heteroatomicligand chromium compound complex having Structure PNPCr2 can be asubstituted 1,2-cyclohexylene, a substituted 1,3-cyclohexylene, asubstituted 1,4-cyclohexylene, a substituted 3,3′-bicyclohexylene, asubstituted 4,4′-bicyclohexylene, a substitutedbis(3-cyclohexylene)methane, a substituted bis(4-cyclohexylene)methane,a substituted 1,2-bis(3-cyclohexylene)ethane, a substituted1,2-bis(4-cyclohexylene)ethane, a substituted1,2-bis(3-cyclohexylene)propane, a substituted1,2-bis(4-cyclohexylene)propane, a substituted2,2-bis(3-cyclohexylene)propane, or a substituted2,2-bis(4-cyclohexylene)propane. In an embodiment, each substituent of asubstituted cyclohexylene, a substituted bis(cyclohexylene)methane, asubstituted bis(cyclohexylene)ethane, or a substituted1,2-bis(3-cyclohexylene)propane which can be utilized as L^(2s) can be ahydrocarbyl group. Substituent groups (general and specific) areindependently disclosed herein and can be utilized without limitation tofurther describe a substituted cyclohexylene (general or specific), asubstituted bis(cyclohexylene)methane (general or specific), asubstituted bis(cyclohexylene)ethane (general or specific), or asubstituted 1,2-bis(3-cyclohexylene)propane (general or specific) whichcan be utilized as L^(2s).

In an embodiment, L^(2s) of the heteroatomic ligand having StructurePNP2 and/or the heteroatomic ligand chromium compound complex havingStructure PNPCr2 can be 1,2-phenylene, a substituted 1,2-phenylene,1,3-phenylene, a substituted 1,3-phenylene, 1,4-phenylene, a substituted1,4-phenylene, 3,3′-biphenylene, a substituted 3,3′-biphenylene,4,4′-biphenylene, a substituted 4,4′-biphenylene,bis(3-phenylene)methane, a substituted bis(3-phenylene)methane,bis(4-phenylene)methane, a substituted bis(4-phenylene)methane,1,2-bis(3-phenylene)ethane, a substituted 1,2-bis(3-phenylene)ethane,1,2-bis(4-phenylene)ethane, a substituted 1,2-bis(4-phenylene)ethane,1,2-bis(3-phenylene)propane, a substituted 1,2-bis(3-phenylene)propane,1,2-bis(4-phenylene)propane, a substituted 1,2-bis(4-phenylene)propane,2,2-bis(3-phenylene)propane, a substituted 2,2-bis(3-phenylene)propane,2,2-bis(4-phenylene)propane, or a substituted2,2-bis(4-phenylene)propane. In some embodiments, L^(2s) of theheteroatomic ligand having Structure PNP2 and/or the heteroatomic ligandchromium compound complex having Structure PNPCr2 can be a substituted1,2-phenylene, a substituted 1,3-phenylene, a substituted 1,4-phenylene,a substituted 3,3′-biphenylene, a substituted 4,4′-biphenylene, asubstituted bis(3-phenylene)methane, a substitutedbis(4-phenylene)methane, a substituted 1,2-bis(3-phenylene)ethane, asubstituted 1,2-bis(4-phenylene)ethane, a substituted1,2-bis(3-phenylene)propane, a substituted 1,2-bis(4-phenylene)propane,a substituted 2,2-bis(3-phenylene)propane, or a substituted2,2-bis(4-phenylene)propane. In an embodiment, each substituent of asubstituted phenylene (general or specific), a substituted biphenylene(general or specific), a substituted bis(phenylene)methane (general orspecific), a substituted bis(phenylene)ethane (general or specific),and/or a substituted bis(phenylene)propane (general or specific) whichcan be utilized as L^(2s) can be a hydrocarbyl group. Substituenthydrocarbyl groups (general and specific) are independently disclosedherein and can be utilized without limitation to further describe asubstituted phenylene (general or specific), a substituted biphenylene(general or specific), a substituted bis(phenylene)methane (general orspecific), a substituted bis(phenylene)ethane(general or specific),and/or a substituted bis(phenylene)propane (general or specific) whichcan be utilized as L²′.

Generally, L^(3s) and L^(4s) of any organylene L^(1s) group disclosedherein, any heteroatomic ligand structure provided herein, and/or anyheteroatomic ligand chromium compound complex structure provided hereinindependently can be an organylene group; alternatively, an organylenegroup consisting of inert functional groups; or alternatively, ahydrocarbylene group. In an embodiment, the organylene group which canbe utilized as L^(3s) and/or L^(4s) can be a C₁ to C₂₀, a C₁ to C₁₅, ora C₁ to C₁₀ organylene group. In an embodiment, the organylene groupconsisting of inert functional groups which can be utilized as L^(3s)and/or L^(4s) can be a C₁ to C₂₀, a C₁ to C₁₅, or a C₁ to C₁₀ organylenegroup consisting of inert functional groups. In an embodiment, thehydrocarbylene group which can be utilized as L^(3s) and/or L^(4s) canbe a C₁ to C₂₀, a C₁ to C₁₅, or a C₁ to C₁₀ hydrocarbylene group. In anembodiment, L^(3s) and L^(4s) of any organylene L^(1s) group disclosedherein, any heteroatomic ligand structure provided herein, and/or anyheteroatomic ligand chromium compound complex structure provided hereinindependently can be a C₁ to C₂₀, C₁ to C₁₅, or a C₁ to C₁₀ alkylenegroup.

In an embodiment, L^(3s) and L^(4s) of any organylene L^(1s) groupdisclosed herein, any heteroatomic ligand structure provided herein,and/or any heteroatomic ligand chromium compound complex structureprovided herein independently can be —(CR^(P)R^(P′))_(m)— where eachR^(P) and R^(P′) can independently be hydrogen, methyl, ethyl, propyl,isopropyl, or butyl groups and m can be an integer from 1 to 12. In someembodiments, L^(3s) and L^(4s) of any organylene L^(1s) group disclosedherein, any heteroatomic ligand structure provided herein, and/or anyheteroatomic ligand chromium compound complex structure provided hereinindependently can be a methylene group (—CH₂—), an eth-1,2-ylene group(—CH₂CH₂—), an ethen-1,2-ylene group (—CH═CH—), a prop-1,3-ylene group(—CH₂CH₂CH₂—), a prop-1,2-ylene group (—CH(CH₃)CH₂—), a prop-2,2-ylenegroup (—C(CH₃)₂—), a 1-methylethen-1,2-ylene group (—C(CH₃)═CH—), abut-1,4-ylene group (—CH₂CH₂CH₂—CH₂—), a but-1,3-ylene group(—CH₂CH₂CH(CH₃)—), a but-2,3-ylene group (—CH(CH₃)CH(CH₃)—), abut-2-en-2,3-ylene group (—C(CH₃)C(CH₃)—), a 3-methylbut-1,3-ylene group(—CH₂CH₂C(CH₃)₂—), a 1,2-cyclopentylene group, a 1,2-cyclohexylenegroup, or a phen-1,2-ylene group; alternatively, a methylene group(—CH₂—), an eth-1,2-ylene group (—CH₂CH₂—), a prop-1,3-ylene group(—CH₂CH₂CH₂—), a prop-1,2-ylene group (—CH(CH₃)CH₂—), a prop-2,2-ylenegroup (—C(CH₃)₂—), a but-1,4-ylene group (—CH₂CH₂CH₂—CH₂—), abut-1,3-ylene group (—CH₂CH₂CH(CH₃)—), a but-2,3-ylene group(—CH(CH₃)CH(CH₃)—), a 1,2-cyclopentylene group, a 1,2-cyclohexylenegroup, or a phen-1,2-ylene group; alternatively, an eth-1,2-ylene group(—CH₂CH₂—), a prop-1,3-ylene group (—CH₂CH₂CH₂—), a prop-1,2-ylene group(—CH(CH₃)CH₂—), a but-1,3-ylene group (—CH₂CH₂CH(CH₃)—), a but-2,3-ylenegroup (—CH(CH₃)CH(CH₃)—), a 1,2-cyclopentylene group, a1,2-cyclohexylene group, or a phen-1,2-ylene group. In some embodiments,L³s and ^(Los) of any organylene L^(1s) group disclosed herein, anyheteroatomic ligand structure provided herein, and/or any heteroatomicligand chromium compound complex structure provided herein independentlycan be an eth-1,2-ylene group (—CH₂CH₂—); alternatively, aprop-1,3-ylene group (—CH₂CH₂CH₂—); alternatively, a prop-1,2-ylenegroup (—CH(CH₃)CH₂—); alternatively, a but-1,3-ylene group(—CH₂CH₂CH(CH₃)—); alternatively, a but-2,3-ylene group(—CH(CH₃)CH(CH₃)—); alternatively, a 1,2-cyclopentylene group;alternatively, a 1,2-cyclohexylene group; or alternatively, aphen-1,2-ylene group.

While not shown, one of ordinary skill in the art will recognize that aneutral ligand can be associated with the chromium compounds orheteroatomic ligand chromium compound complexes described herein.Additionally it should be understood that while chromium compounds orheteroatomic ligand chromium compound complexes provided herein do notformally show the presence of a neutral ligand, the chromium compoundsor heteroatomic ligand chromium compound complexes having neural ligands(e.g., nitriles and ethers, among others) are fully contemplated aspotential chromium compounds or heteroatomic ligand chromium compoundcomplexes that can be utilized in the catalyst system used in aspectsand embodiments of the herein described inventions.

In a non-limiting embodiment, the heteroatomic ligand can be any one ormore of HL 1, HL 2, HL 3, HL 4. HL 5, HL 6, HL 7, HL 7, and HL 9. Insome non-limiting embodiments, the diphosphino amine transition metalcompound complex can be a chromium compound complex of any one or moreof HLCr 1, HLCr 2, HLCr 3, HLCr 4, HLCr 5, HLCr 6, HLCr 7, HLCr 8, andHLCr 9. In other non-limiting embodiments, the diphosphino aminetransition metal compound complex can be a chromium(III) chloride orchromium(III) acetylacetonate complex of any one or more of HLCr 1, HLCr2, HLCr 3, HLCr 4, HLCr 5, HLCr 6, HLCr 7, HLCr 8, and HLCr 9.

Generally, the aluminoxane utilized in the catalyst systems which areutilized in the processes, systems, and/or reaction systems disclosedherein can be any aluminoxane which can, in conjunction with thechromium compound complexes and the heteroatomic ligand or alternativelythe heteroatomic ligand chromium compound complex, catalyze theformation of an ethylene oligomer product. In a non-limiting embodiment,the aluminoxane can have a repeating unit characterized by the FormulaI:

wherein R′ is a linear or branched alkyl group. Alkyl groups for metalalkyl compounds are independently described herein and can be utilizedwithout limitation to further describe the aluminoxanes having FormulaI. Generally, n of Formula I can be greater than 1; or alternatively,greater than 2. In an embodiment, n can range from 2 to 15; oralternatively, range from 3 to 10.

In an aspect, each alkyl group of the aluminoxane independently can be,comprise, or consist essentially of, a C₁ to C₂₀ alkyl group;alternatively, a C₁ to C₁₀ alkyl group; or alternatively, a C₁ to C₆alkyl group. In an embodiment, each alkyl group of the aluminoxaneindependently can be, comprise, or consist essentially of, a methylgroup, an ethyl group, a propyl group, a butyl group, a pentyl group, ahexyl group, a heptyl group, or an octyl group; alternatively, a methylgroup, a ethyl group, a butyl group, a hexyl group, or an octyl group.In some embodiments, each alkyl group or the aluminoxane independentlycan be, comprise, or consist essentially of, a methyl group, an ethylgroup, an n-propyl group, an n-butyl group, an iso-butyl group, ann-hexyl group, or an n-octyl group; alternatively, a methyl group, anethyl group, an n-butyl group, or an iso-butyl group; alternatively, amethyl group; alternatively, an ethyl group; alternatively, an n-propylgroup; alternatively, an n-butyl group; alternatively, an iso-butylgroup; alternatively, an n-hexyl group; or alternatively, an n-octylgroup.

In a non-limiting embodiment, the aluminoxane can be, comprise, orconsist essentially of, methylaluminoxane (MAO), ethylaluminoxane,modified methylaluminoxane (MMAO), n-propylaluminoxane,iso-propyl-aluminoxane, n-butylaluminoxane, sec-butylaluminoxane,iso-butylaluminoxane, t-butylaluminoxane, 1-pentyl-aluminoxane,2-entylaluminoxane, 3-pentyl-aluminoxane, iso-pentyl-aluminoxane,neopentylaluminoxane, or mixtures thereof. In some non-limitingembodiments, the aluminoxane can be, comprise, or consist essentiallyof, methylaluminoxane (MAO), modified methylaluminoxane (MMAO), isobutylaluminoxane, t-butyl aluminoxane, or mixtures thereof. In othernon-limiting embodiments, the aluminoxane can be, comprise, or consistessentially of, methylaluminoxane (MAO); alternatively,ethylaluminoxane; alternatively, modified methylaluminoxane (MMAO);alternatively, n-propylaluminoxane; alternatively,iso-propyl-aluminoxane; alternatively, n-butylaluminoxane;alternatively, sec-butylaluminoxane; alternatively,iso-butylaluminoxane; alternatively, t-butyl aluminoxane; alternatively,1-pentyl-aluminoxane; alternatively, 2-pentylaluminoaxne; alternatively,3-pentyl-aluminoxane; alternatively, iso-pentyl-aluminoxane; oralternatively, neopentylaluminoxane.

The scrub agent which can be utilized in aspects and embodiments of anyof the processes, systems, and/or reaction systems described herein canbe any compound(s) which can remove water, oxygen, and/or other speciesdetrimental to the ability of the catalyst system to oligomerizeethylene. In some embodiments, the scrub agent can be an organoaluminumcompound. In an embodiment, the organoaluminum compound can be analkylaluminum compound. In an embodiment, the alkylaluminum compound canbe a trialkylaluminum, an alkylaluminum halide, an alkylaluminumalkoxide, or any combination thereof. In some embodiments, thealkylaluminum compound can be a trialkylaluminum, an alkylaluminumhalide, or any combination thereof; alternatively, a trialkylaluminum,an alkylaluminum halide, or any combination thereof; or alternatively, atrialkylaluminum. In other embodiments, the alkylaluminum compound canbe a trialkylaluminum; alternatively, an alkylaluminum halide; oralternatively, an alkylaluminum alkoxide. In yet other embodiments, thealkylaluminum compound which can be utilized as the scrub agent can bean aluminoxane (described herein). In a non-limiting embodiment, thetrialkylaluminum compound can be, comprise, or consist essentially of,trimethylaluminum, triethylaluminum, tripropylaluminum,tributylaluminum, trihexylaluminum, trioctylaluminum, or mixturesthereof. In some non-limiting embodiments, the trialkylaluminum compoundcan be, comprise, or consist essentially of, trimethylaluminum,triethylaluminum, tripropylaluminum, tri-n-butylaluminum,tri-isobutylaluminum, trihexylaluminum, tri-n-octylaluminum, or mixturesthereof; alternatively, triethylaluminum, tri-n-butylaluminum,tri-isobutylaluminum, trihexylaluminum, tri-n-octylaluminum, or mixturesthereof; alternatively, triethylaluminum, tri-n-butylaluminum,trihexylaluminum, tri-n-octylaluminum, or mixtures thereof. In othernon-limiting embodiments, the trialkylaluminum compound can be,comprise, or consist essentially of, trimethylaluminum; alternatively,triethylaluminum; alternatively, tripropylaluminum; alternatively,tri-n-butylaluminum; alternatively, tri-isobutylaluminum; alternatively,trihexylaluminum; or alternatively, tri-n-octylaluminum. In anon-limiting embodiment, the alkylaluminum halide can be, comprise, orconsist essentially of, diethylaluminum chloride, diethylaluminumbromide, ethylaluminum dichloride, ethylaluminum sesquichloride, ormixtures thereof. In some non-limiting embodiments, the alkylaluminumhalide can be, comprise, or consist essentially of, diethylaluminumchloride, ethylaluminum dichloride, ethylaluminum sesquichloride, ormixtures thereof. In other non-limiting embodiments, the alkylaluminumhalide can be, comprise, or consist essentially of, diethylaluminumchloride; alternatively, diethylaluminum bromide; alternatively,ethylaluminum dichloride; or alternatively, ethylaluminumsesquichloride. In particular aspects of this invention, theorganoaluminum compound can comprise trimethylaluminum (TMA),triethylaluminum (TEA), tri-n-propylaluminum (TNPA), tri-n-butylaluminum(TNBA), triisobutylaluminum (TIBA), tri-n-hexylaluminum,tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminumethoxide, diethylaluminum chloride, or combinations thereof.

In an embodiment, the alkylaluminum compound which can be utilized asthe scrub agent can be an aluminoxane. Aluminoxanes are independentlydisclosed herein (e.g., as a component of the catalyst system) and anyof the general or specific aluminoxanes disclosed herein can be utilizedwithout limitation as the scrub agent utilized in the processes, systemsand/or reaction systems disclosed herein.

The herein described scrub agent optionally can be indirectly introducedto the reaction zone 110 from a scrub agent source 170 via feed line172. The scrub agent feed line 172, when present in system 100, 200, or300, is defined as having at least one scrub agent.

Generally, the ethylene oligomer product that can be produced using theprocesses, systems, and/or reaction system described herein can beformed at conditions (or alternatively, the reaction zone 110 can haveany conditions) which can 1) facilitate ethylene oligomer productformation, 2) provide a desired ethylene oligomer product formationrate, 3) provide acceptable catalyst system productivity, 4) provideacceptable oligomer selectivity, and/or 5) provide acceptable polymerformation. In an embodiment, conditions under which the ethyleneoligomer product can be formed (or alternatively, the reaction zone canhave any conditions) can include one or more of catalyst systemcomponent ratios, chromium concentration, pressure, ethylene partialpressure, ethylene concentration, presence of hydrogen (and its partialpressure and/or hydrogen to ethylene weight ratio), temperature,reaction time, single pass ethylene conversion, and catalyst systemproductivity. Catalyst system component ratios, chromium concentration,pressure, ethylene partial pressure, ethylene concentration, presence ofhydrogen (and its partial pressure and/or hydrogen to ethylene weightratio), temperature, reaction time, single pass ethylene conversion, andcatalyst system productivity are independently described herein andthese independent descriptions can be used without limitation and in anycombination to describe the process, system, or reaction zone conditionsat which the ethylene oligomer product can be formed for any of theprocesses, systems, and/or reaction systems described herein.

In an embodiment, the ethylene oligomer product can be formed (or thereaction zone can operate) at a minimum aluminum of the aluminoxane tochromium of the chromium component (e.g., the chromium compound or theheteroatomic ligand chromium compound complex) molar ratio (i.e.,minimum Al to Cr molar ratio) of 10:1, 50:1, 75:1, or 100:1;alternatively or additionally, at a maximum aluminum of the aluminoxaneto chromium of the chromium component (e.g., the chromium compound orthe heteroatomic ligand chromium compound complex) molar ratio (i.e.,maximum Al to Cr molar ratio) of 5,000:1, 3,000:1, 2,000:1, 1,500:1, or1,000:1. In an embodiment, the ethylene oligomer product can be formed(or the reaction zone can operate) at an Al to Cr molar ratio rangingfrom any minimum Al to Cr molar ratio disclosed herein to any maximum Alto Cr molar ratio disclosed herein. In a non-limiting embodiment, the Alto Cr molar ratio can range from 10:1 to 5,000:1, from 50:1 to 3,000:1,from 50:1 to 3,000:1, from 75:1 to 2,000:1, from 100:1 to 2,000:1, offrom 100:1 to 1,000:1. Other Al to Cr molar ratio ranges that can beutilized are readily apparent to those skilled in the art with the aidof this disclosure.

In an embodiment, the ethylene oligomer product can be formed (or thereaction zone can operate) at a minimum heteroatomic ligand to chromiumcompound (either as the chromium compound of as the chromium compound ofthe heteroatomic ligand chromium compound complex) equivalent ratio(i.e., minimum heteroatomic ligand to Cr equivalent ratio) of 0.8:1,0.9:1, or 0.95:1; alternatively or additionally, at a maximumheteroatomic ligand to chromium compound (either as the chromiumcompound of as the chromium compound of the heteroatomic ligand chromiumcompound complex) equivalent ratio (i.e., minimum heteroatomic ligand toCr equivalent ratio) of 5:1, 4:1, 3:1, or 2.5:1. In an embodiment, theethylene oligomer product can be formed (or the reaction zone canoperate) at an heteroatomic ligand to Cr equivalent ratio ranging fromany minimum heteroatomic ligand to Cr equivalent ratio disclosed hereinto any maximum heteroatomic ligand to Cr equivalent ratio disclosedherein. In a non-limiting embodiment, the heteroatomic ligand to Crmolar ratio can range from 0.8:1 to 5:1, from 0.9:1 to 4:1, from 0.90:1to 3:1, from 0.95:1 to 3:1, or from 0.95:1 to 2.5:1. Other heteroatomicligand to Cr equivalent ratio ranges that can be utilized are readilyapparent to those skilled in the art with the aid of this disclosure.

In an embodiment, the ethylene oligomer product can be formed (or thereaction zone can operate) at a minimum reaction zone chromiumconcentration of the chromium component (e.g., the chromium compound orthe heteroatomic ligand chromium compound complex) concentration (i.e.,minimum chromium concentration) of 1×10⁻⁶ Cr equivalents/liter, 1×10⁻⁵Cr equivalents/liter, or 5×10⁻⁴ Cr equivalents/liter; alternatively oradditionally, at a maximum reaction zone chromium concentration of thechromium component (e.g., the chromium compound or the heteroatomicligand chromium compound complex) of 1 Cr equivalents/liter, 5×10⁻¹ Crequivalents/liter, or 1×10⁻¹ Cr equivalents/liter. In an embodiment, theethylene oligomer product can be formed (or the reaction zone canoperate) at a reaction zone chromium concentration ranging from anyminimum chromium concentration disclosed herein to any maximum chromiumconcentration disclosed herein. In a non-limiting embodiment, thereaction zone chromium concentration can range from 1×10⁻⁶ Crequivalents/liter to 1 Cr equivalents/liter, from 1×10⁻⁵ Crequivalents/liter to 5×10⁻¹ Cr equivalents/liter, from 5×10⁻⁴ Crequivalents/liter to 1×10⁻¹ Cr equivalents/liter. Other chromiumconcentration ranges that can be utilized are readily apparent to thoseskilled in the art with the aid of this disclosure.

In an embodiment, the ethylene oligomer product can be formed (or thereaction zone can operate) at a minimum pressure of 5 psi (34.5 kPa), 50psi (345 kPa); 100 psi (689 kPa), 150 psi (1.03 MPa), 250 psi (1.72MPa), 500 psi (3.5 MPa), or 600 psi (4.1 MPa); alternatively oradditionally, at a maximum pressure of 2,500 psi (17.2 MPa), 2,000 psi(13.8 MPa), 1,500 psi (10.3 MPa), 1400 psi (9.65 MPa), 1250 psi (8.62MPa), or 1000 psi (6.89 MPa). In an embodiment, the ethylene oligomerproduct can be formed (or the reaction zone can operate) at a pressureranging from any minimum pressure disclosed herein to any maximumpressure disclosed herein. In some non-limiting embodiments, theethylene oligomer product can be formed (or the reaction zone canoperate) at a pressure from 5 psi (34.5 kPa) to 2,500 psi (17.2 MPa),from 5 psi (34.5 kPa) to 2,000 psi (13.8 MPa), from 50 psi (345 kPa) to2,000 psi (13.8 MPa), from 100 psi (689 kPa) to 2,000 psi (13.8 MPa),from 100 psi (689 kPa) to 1,500 psi (10.3 MPa), from 500 psi (3.5 MPa)to 1500 psi (10.3 MPa), from 150 psi (1.03 MPa) to 1250 psi (8.62 MPa),from 250 psi (1.72 MPa) to 1000 psig (6.89 MPa), or from 600 psi (4.1MPa) to 1400 psi (9.65 MPa) . Other pressure ranges that can be utilizedare readily apparent to those skilled in the art with the aid of thisdisclosure.

In an embodiment, the ethylene oligomer product can be formed (or thereaction zone can operate) at a minimum ethylene partial pressure of 5psi (34.5 kPa), 50 psi (345 kPa); 100 psi (689 kPa), 150 psi (1.03 MPa),250 psi (1.72 MPa), or 500 psi (3.5 MPa); alternatively or additionallyat a maximum ethylene partial pressure of 2,500 psi (17.2 MPa), 2,000psi (13.8 MPa), 1,500 psi (10.3 MPa), 1250 psi (8.62 MPa), or 1000 psi(6.89 MPa). In an embodiment, the ethylene oligomer product can beformed (or the reaction zone can operate) at an ethylene partialpressure ranging from any minimum ethylene partial pressure disclosedherein to any maximum ethylene partial pressure disclosed herein. Insome non-limiting embodiments, the ethylene oligomer product can beformed (or the reaction zone 110 can operate) at an ethylene partialpressure from 5 psi (34.5 kPa) to 2,500 psi (17.2 MPa), from 5 psi (34.5kPa) to 2,000 psi (13.8 MPa), from 50 psi (345 kPa) to 2,000 psi (13.8MPa), from 100 psi (689 kPa) to 2,000 psi (13.8 MPa), from 100 psi (689kPa) to 1,500 psi (10.3 MPa), from 500 psi (3.5 MPa) to 1500 psi (10.3MPa), from 150 psi (1.03 MPa) to 1250 psi (8.62 MPa), from 150 psi (1.03MPa) to 1250 psi (8.62 MPa), or from 250 psi (1.72 MPa) to 1000 psi(6.89 MPa). Other ethylene partial pressure ranges are readily apparentto those skilled in the art with the aid of this disclosure.

In an embodiment, the ethylene oligomer product can be formed (or thereaction zone can operate) at a minimum ethylene concentration of 4 mass%, 10 mass %, 25 mass %, 35 mass %, or 40 mass % based upon the totalmass in the reaction zone; alternatively or additionally, at a maximumethylene concentration of 70 mass %, 65 mass %, 60 mass %, 55 mass %, 50mass %, 48 mass % based upon the total mass in the reaction zone. In anembodiment, the ethylene oligomer product can be formed (or the reactionzone can operate) at an ethylene concentration ranging from any minimumethylene concentration disclosed herein to any maximum ethyleneconcentration disclosed herein. In some non-limiting embodiments, theethylene oligomer product can be formed (or the reaction zone canoperate) at an ethylene concentration from 4 mass % to 70 mass %, from 4mass % to 60 mass %, from 10 mass % to 60 mass %, from 25 mass % to 55mass %, 35 mass % to 50 mass %, or 40 mass % to 48 mass % based upon thetotal mass in the reaction zone. Other ethylene concentration rangesthat can be utilized are readily apparent to those skilled in the artwith the aid of this disclosure.

In an embodiment, the ethylene oligomer product can be formed (or thereaction zone can operate) at a minimum ethylene:chromium mass ratio of50,000:1, 150,000:1, 250,000:1, or 400,000:1; alternatively oradditionally, at a maximum ethylene:chromium mass ratio of 5,000,000:1,2,500,000:1, 1,500,000:1, or 1,000,000:1. In an embodiment, the ethyleneoligomer product can be formed (or the reaction zone can operate) at anethylene:chromium mass ratio ranging from any minimum ethylene:chromiummass ratio disclosed herein to any maximum ethylene:chromium mass ratiodisclosed herein. In some non-limiting embodiments, the ethyleneoligomer product can be formed (or the reaction zone can operate) at anethylene:chromium mass ratio from 50,000:1 to 5,000,000:1, 150,000:1 to2,500,000:1, 250,000:1 to 1,500,000:1, or 400,000:1 to 1,000,000:1.Other ethylene:chromium mass ratio ranges that can be utilized arereadily apparent to those skilled in the art with the aid of thisdisclosure.

In an embodiment wherein hydrogen is utilized, the ethylene oligomerproduct can be formed (or the reaction zone can operate) at a minimumhydrogen partial pressure of 1 psi (6.9 kPa), 2 psi (14 kPa); 5 psi (34kPa), 10 psi (69 kPa), or 15 psi (103 kPa); alternatively oradditionally at a maximum hydrogen partial pressure of 200 psi (1.4MPa), 150 psi (1.03 MPa), 100 psi (689 kPa), 75 psig (517 kPa), or 50psi (345 kPa). In an embodiment, the ethylene oligomer product can beformed (or the reaction zone can operate) at a hydrogen partial pressureranging from any minimum hydrogen partial pressure disclosed herein toany maximum hydrogen partial pressure disclosed herein. In somenon-limiting embodiments wherein hydrogen is utilized, the ethyleneoligomer product can be formed (or the reaction zone can operate) at ahydrogen partial pressure from 1 psi (6.9 kPa) to 200 psi (1.4 MPa),from 5 psi (34 kPa) to 150 psi (1.03 MPa), from 10 psi (69 kPa) to 100psi (689 kPa), or from 15 psi (100 kPa) to 75 psig (517 kPa). Otherhydrogen partial pressure ranges that can be utilized are readilyapparent to those skilled in the art with the aid of this disclosure.

In an embodiment wherein hydrogen is utilized, the ethylene oligomerproduct can be formed (or the reaction zone can operate) at a minimumhydrogen to ethylene mass ratio of (0.05 g hydrogen)/(kg ethylene), (0.1g hydrogen)/(kg ethylene), (0.25 g hydrogen)/(kg ethylene), (0.4 ghydrogen)/(kg ethylene), or (0.5 g hydrogen)/(kg ethylene);alternatively or additionally, at a maximum hydrogen to ethylene massratio can be (5 g hydrogen)/(kg ethylene), (3 g hydrogen)/(kg ethylene),(2.5 g hydrogen)/(kg ethylene), (2 g hydrogen)/(kg ethylene), or (1.5 ghydrogen)/(kg ethylene). In an embodiment, the ethylene oligomer productcan be formed (or the reaction zone can operate) at a hydrogen toethylene mass ratio ranging from any minimum hydrogen to ethylene massratio disclosed herein to any maximum hydrogen to ethylene mass ratiodisclosed herein. In some non-limiting embodiments, the ethyleneoligomer product can be formed (or the reaction zone can operate) at ahydrogen to ethylene mass ratio from (0.05 g hydrogen)/(kg ethylene) to(5 g hydrogen)/(kg ethylene), from (0.25 g hydrogen)/(kg ethylene) to (5g hydrogen)/(kg ethylene), from (0.25 g hydrogen)/(kg ethylene) to (4 ghydrogen)/(kg ethylene), from (0.4 g hydrogen)/(kg ethylene) to (3 ghydrogen)/(kg ethylene), from (0.4 g hydrogen)/(kg ethylene) to (2.5 ghydrogen)/(kg ethylene), from (0.4 g hydrogen)/(kg ethylene) to (2 ghydrogen)/(kg ethylene), or from (0.5 g hydrogen)/(kg ethylene) to (2 ghydrogen)/(kg ethylene). Other hydrogen to ethylene mass ratio rangesthat can be utilized are readily apparent to those skilled in the artwith the aid of this disclosure

In an embodiment, the ethylene oligomer product can be formed (or thereaction zone can operate) at a minimum hydrogen:chromium mass ratio of1:1, 50:1, 100:1, or 200:1; alternatively or additionally at a maximumhydrogen:chromium mass ratio of 100,000:1, 50,000:1, 10,000:1, or3,000:1. In an embodiment, the ethylene oligomer product can be formed(or the reaction zone can operate) at a hydrogen:chromium mass ratioranging from any minimum hydrogen:chromium mass ratio disclosed hereinto any maximum hydrogen:chromium mass ratio disclosed herein. In somenon-limiting embodiments, the ethylene oligomer product can be formed(or the reaction zone can operate) at a hydrogen:chromium mass ratiofrom 1:1 to 100,000:1, 50:1 to 50,000:1, 100:1 to 10,000:1, or 200:1 to3,000:1. Other hydrogen:chromium mass ratio ranges that can be utilizedare readily apparent to those skilled in the art with the aid of thisdisclosure.

In an embodiment, the ethylene oligomer product can be formed (or thereaction zone can operate) at a minimum temperature of 0° C., 25° C.,40° C., or 50° C.; alternatively or additionally at a maximumtemperature of 200° C., 150° C., 100° C., or 90° C. In an embodiment,the ethylene oligomer product can be formed (or the reaction zone canoperate) at a temperature ranging from any minimum temperature disclosedherein to any maximum temperature disclosed herein. In some non-limitingembodiments, the ethylene oligomer product can be formed (or thereaction zone can operate) at a temperature from 0° C. to 200° C., from25° C. to 150° C., from 40° C. to 100° C., from 50° C. to 100° C., orfrom 50° C. to 90° C. Other temperature ranges that can be utilized arereadily apparent to those skilled in the art with the aid of thisdisclosure.

The reaction time (or residence time), for example, in the reaction zonecan comprise any time that can produce the desired quantity of ethyleneoligomer product; alternatively, any reaction time (or residence time)that can provide a desired catalyst system productivity; alternatively,any reaction time (or residence time) that can provide a desiredethylene conversion. Relating to forming the ethylene oligomer product,the ethylene oligomer product can be formed over a period of time (or anaverage time) that can produce the desired quantity of olefin product orpolymer product, provide a desired catalyst system productivity, and/orprovide a desired conversion of monomer. In some embodiments, the timecan range from 1 minute to 5 hours; alternatively, ranges from 5 minutesto 2.5 hours; alternatively, ranges from 10 minutes to 2 hours; oralternatively, ranges from 15 minutes to 1.5 hours. In some embodiments(in continuous process embodiments), the reaction time (or residencetime) can be stated as an average reaction time (or average residencetime) and can range from 1 minute to 5 hours; alternatively, ranges from5 minutes to 2.5 hours; alternatively, ranges from 10 minutes to 2hours; or alternatively, ranges from 15 minutes to 1.5 hours.

In an embodiment, the processes, systems, and/or reaction systemsdescribed herein can have and ethylene conversion of at least 30%, 35%,40%, or 45%.

In an embodiment, the processes, systems, and/or reactions systemsdescribed herein can have a catalyst system productivity of greater than10,000, 50,000,100,000, 150,000, 200,000, 300,000, or 400,000 grams(C₆+C₈) per gram of chromium. In some embodiments (but not necessarilyall embodiments), the processes, systems, and/or reaction systemsdescribed herein can have a productivity higher than a productivity inan otherwise similar process which does not contact ethylene with the atleast a portion of the organic reaction medium prior to contact ofethylene with the catalyst system; alternatively, does not introduce orfeed the feedstock mixture into the reaction zone separately from thecatalyst system; or alternatively, productivity higher than aproductivity in an otherwise similar process which does not: i) contactethylene with the at least a portion of the organic reaction mediumprior to contact of ethylene with the catalyst system, and/or ii)introduce or feed the feedstock mixture into the reaction zoneseparately from the catalyst system. In an embodiment (but not allembodiments), the productivity can increased by 5%, 7.5%, 10%, or 12.5%.

In some aspects and embodiments (but not necessarily all aspects and/orembodiments), the processes, systems, and reaction systems describedherein can produce less polymer per gram of ethylene oligomer productthan an otherwise similar process which does not contact ethylene withthe at least a portion of the organic reaction medium prior to contactof ethylene with the catalyst system; alternatively, does not introduceor feed the feedstock mixture into the reaction zone separately from thecatalyst system; or alternatively, produce less polymer per gram ofethylene oligomer product than an otherwise similar process which doesnot: i) contact ethylene with the at least a portion of the organicreaction medium prior to contact of ethylene with the catalyst system,and/or ii) introduce or feed the feedstock mixture into the reactionzone, e.g., reaction zone 110, separately from the catalyst system. Inan embodiment (but not all embodiments), the mass of polymer per mass ofoligomer in the reaction zone can decrease by 10%, 25%, 40%, 50%, 60%,70%, or 80%.

Depending upon the catalyst system utilized, the processes, systems,and/or reaction systems described herein can be an ethyleneoligomerization process, system, and/or reaction system, an ethylenetrimerization process, system, or reaction system, an ethylenetetramerization process, system, or reaction system or an ethylenetrimerization and tetramerization process system, or reaction system;alternatively, an ethylene oligomerization process system, or reactionsystem; alternatively, an ethylene trimerization process, system, orreaction system; alternatively, an ethylene tetramerization process,system, or reaction system; or alternatively an ethylene trimerizationand tetramerization process, system, or reaction system. In an ethylenetrimerization embodiment, the ethylene oligomer product can comprise atleast 70 wt. % hexenes, at least 75 wt. % hexenes, at least 80 wt. %hexenes, at least 85 wt. % hexenes, or at least 90 wt. % hexene basedupon the weight of the ethylene oligomer product. In some ethylenetrimerization embodiments, the ethylene oligomer product can comprisefrom 70 wt. % to 99.8 wt. % hexenes, from 75 wt. % to 99.7 wt. %hexenes, or from 80 wt. % to 99.6 wt. % hexenes based upon the weight ofthe ethylene oligomer product. In an ethylene tetramerizationembodiment, the ethylene oligomer product can comprise at least 70 wt. %octene, at least 75 wt. % octene, at least 80 wt. % octenes, at least 85wt. % octenes, or at least 90 wt. % octenes based upon the weight of theethylene oligomer product. In some ethylene tetramerization embodiments,the ethylene oligomer product can comprise from 70 wt. % to 99.8 wt. %octenes, from 75 wt. % to 99.7 wt. % octenes, or from 80 wt. % to 99.6wt. % octenes based upon the weight of the ethylene oligomer product. Inan ethylene trimerization and tetramerization embodiment, the ethyleneoligomer product can comprise at least 70 wt. % hexenes and octenes, atleast 75 wt. % hexenes and octenes, at least 80 wt. % hexenes andoctenes, at least 85 wt. % hexene and octene, or at least 90 wt. %hexenes and octenes based upon the weight of the ethylene oligomerproduct. In some ethylene trimerization and tetramerization embodiments,the ethylene oligomer product can comprise from 70 wt. % to 99.8 wt. %hexenes and octenes, from 75 wt. % to 99.7 wt. % hexenes and octenes, orfrom 80 wt. % to 99.6 wt. % hexenes and octenes based upon the weight ofthe ethylene oligomer product.

In ethylene oligomerization, ethylene trimerization, or ethylenetrimerization and tetramerization embodiments, the ethylene trimer cancomprise at least 85 wt. % 1-hexene; alternatively, at least 87.5 wt. %1-hexene; alternatively, at least 90 wt. % 1-hexene; alternatively, atleast 92.5 wt. % 1-hexene; alternatively, at least 95 wt. % 1-hexene;alternatively, at least 97 wt. % 1-hexene; or alternatively, at least 98wt. % 1-hexene by weight of the ethylene trimer, or from 85 wt. % to99.9 wt. % 1-hexene; alternatively, from 87.5 wt. % to 99.9 wt. %1-hexene; alternatively, from 90 wt. % to 99.9 wt. % 1-hexene;alternatively, from 92.5 wt. % to 99.9 wt. % 1-hexene; alternatively,from 95 wt. % to 99.9 wt. % 1-hexene; alternatively, from 97 wt. % to99.9 wt. % 1-hexene; or alternatively, from 98 wt. % to 99.9 wt. %1-hexene by weight of the ethylene trimer.

In ethylene oligomerization, ethylene tetramerization, or ethylenetrimerization and tetramerization embodiments, the ethylene tetramer cancomprise at least 85 wt. % 1-octene; alternatively, at least 87.5 wt. %1-octene; alternatively, at least 90 wt. % 1-octene; alternatively, atleast 92.5 wt. % 1-octene; alternatively, at least 95 wt. % 1-octene;alternatively, at least 97 wt. % 1-octene; or alternatively at least 98wt. % 1-octene by weight of the ethylene tetramer or from 85 wt. % to99.9 wt. % 1-octene; alternatively, from 87.5 wt. % to 99.9 wt. %1-octene; alternatively, from 90 wt. % to 99.9 wt. % 1-octene;alternatively, from 92.5 wt. % to 99.9 wt. % 1-octene; alternatively,from 95 wt. % to 99.9 wt. % 1-octene; alternatively, from 97 wt. % to99.9 wt. % 1-octene; or alternatively, from 98 wt. % to 99.9 wt. %1-octene by weight of the ethylene tetramer.

The processes, systems, and/or reaction systems described herein canprovide various advantages. Without being limited to theory, it isbelieved that the presence of a C₃₊ olefin during the initial startup ofoligomerization processes, systems, and/or reaction systems can decreasethe mass of polymer during the startup of a selective oligomerizationprocess, system, and/or reaction system. This reduction in the mass ofpolymer during startup of oligomerization processes, systems, and/orreaction systems described herein can lead to improved process, system,and/or reaction system operability and/or productivity. Another sourceof polymer formation can result when high concentrations of ethylenecontact the catalyst system. The processes, systems, and/or reactionsystems (e.g., reaction systems 100, 200, and/or 300) described hereincan reduce the amount of polymer formed by the use of a C₃₊ olefinduring the initial stages of ethylene oligomerization and/or contactingethylene with at least a portion of the organic reaction medium prior toethylene contacting the catalyst system. For example, the mass ofundesirable polymer (e.g., polyethylene in contrast to desired oligomersof ethylene) per mass of oligomer formed in the reaction zone (e.g.,reaction zone 110 in systems 100, 200, and 300) can be less than a massof polymer per mass of oligomer in the reaction zone of otherwisesimilar processes, systems, and/or reaction systems where the reactionzone C₃₊ olefin:ethylene weight ratio does not decrease over the periodof time.

Additionally, the mass of polymer (e.g., polyethylene in contrast todesired oligomers of ethylene) per mass of oligomer in the reaction zone(e.g., reaction zone 110 the processes, systems, and/or reactionssystems (e.g., reaction system 200 and 300) can be less than a mass ofpolymer per mass of oligomer in the reaction zone of otherwise similarsystems or process which do not include contacting ethylene with atleast a portion of the organic reaction medium prior to contact ofethylene with the catalyst systems disclosed herein. The mass of polymerper mass of oligomer in the reaction zone (e.g., reaction zone 110) forthe processes, systems, and/or reaction systems (e.g., reaction systems200 and 300) can be less than a mass of polymer per mass of oligomer inthe reaction zone of an otherwise similar system or process which doesnot introduce or feed the feedstock mixture to the reaction zoneseparately from the catalyst systems disclosed herein.

Additionally, the productivity of the processes, system, and/or reactionsystems (e.g., reaction systems 100, 200, and 300) can be higher thanother similar processes, systems, and/or reaction system where the C₃₊olefin is not introduced to the reaction zone 110 and/or ethylene isintroduced into the reaction zone 110 which does not contain C₃₊ olefin.Productivity is defined as the mass of liquid ethylene oligomer product(or alternatively, C₆ product, C₈ product, or (C₆+C₈) product) formedper mass of chromium or aluminum.

Additionally, the productivity of the processes, systems, and/orreaction systems (e.g., reaction systems 200 and 300) and processes,systems, and/or reaction systems can be greater than other similarsystems and processes which do not contact ethylene with at least aportion of the organic reaction medium prior to contact of ethylene withthe catalyst systems disclosed herein. The productivity of theprocesses, systems, and/or reaction systems (e.g., reaction systems 200and 300) can be greater than other similar processes, systems, and/orreaction systems which do not introduce or feed the feedstock mixture tothe reaction zone 110 separately from the catalyst systems disclosedherein.

The disclosed processes, systems, and/or reaction systems can provideimproved commercial applicability for the use of catalysts systems inethylene oligomerization. While not wishing to be bound by theory, it isbelieved that longer operating times are possible because the disclosedsystems and processes can reduce polymerization during oligomerization,thus reducing the levels of problematic fouling and plugging which canoccur in oligomerization reactor components.

Further, the disclosed systems and processes provide improved ethyleneutilization as indicated by improved ethylene conversion and higher C₆purity in the ethylene oligomer product.

PROPHETIC EXAMPLES

The subject matter having been generally described, the followingexamples are given as particular aspects of the disclosure and todemonstrate the practice and advantages thereof. It is understood thatthe examples are given by way of illustration and are not intended tolimit the specification of the claims to follow in any manner.

The catalyst system would be prepared in a dry box by mixing 36 mg ofChromium Component I into 6 mL of ethylbenzene and stirring until thechromium component would be fully dissolved. The aluminoxane MMAO-3A (7wt. % Al) would then be added to the chromium component/ethylbenzenemixture in an amount to achieve an Al:Cr molar ratio of approximately800:1 and would be mixed for 5 to 10 minutes. The chromiumcomponent/ethylbenzene/aluminoxane mixture would then be diluted withmethyl cyclohexane (MCH) in a charger vessel to provide a catalystsystem mixture having a chromium component concentration of 0.025 mg/mL.The charger vessel would then be removed from the drybox and would beattached to feed line 152.

Table 1 below shows a summary of the prophetic operating parameters foroligomerization of ethylene in Examples 1 to 2:

TABLE 1 Prophetic Operating Parameters Example 1 Example 2 Temperature(° C.) 70 70 Pressure (psig; MPag) 900; 6.21 900; 6.21 Organic ReactionMedium Cyclohexane Cyclohexane Organic Reaction Medium Feed Rate (g/h)400 400 Hydrogen Feed Rate (sccm) 24 24 Catalyst System Feed Rate (mL/h)15.7 15.7

In Table 1 and the other tables included herein, use of “g” refers tograms, “h” refers to hours, “mL” refers to milliliters, “min” refers tominutes, “sccm” refers to standard cubic centimeters per minute, “MPag”refers to megapascals gauge, and “psig” refers to pounds per square inchgauge.

The organic reaction medium (cyclohexane) would be treated with molesieves and copper oxide prior to being used for the ethyleneoligomerization.

PROPHETIC EXAMPLE 1 (COMPARATIVE)

In Example 1 (comparative), the oligomerization of ethylene would beperformed without using C₃₊ olefin in the reaction zone during reactionzone startup. The maximum flow rate of ethylene in Example 1 would be200 g/h.

A 300 cc autoclave reactor having the feed line configurations shown inFIG. 2 would be used as the reaction zone 110 and reaction system forExample 1. Although the system 200 of FIG. 2 would be used for Example1, the lines 146 and 147 a-f, which can provide C₃₊ olefin, would not beused in Example 1. That is, a C₃₊ olefin would not be utilized inExample 1 for comparison purposes to Example 2. As can be seen in FIG.2, the ethylene feed line 142 would join with the organic reactionmedium feed line 162 to yield the feedstock mixture feed line 191, whichwould flow through a mixing device 190 (which would be a static mixer).Dispersed feedstock mixture would leave the mixing device 190 in line192, which would feed to the reaction zone 110 via second reaction zoneinlet 113. The catalyst system feed line 152 would feed to the reactionzone 110 via first reaction zone inlet 111 without any combination withother streams or dilution. For Example 1, the control valve 130 shown inFIG. 2 would be a pair of control valves placed in parallel flow, withthe second valve of the two control valves being used only upon pluggingof the first control valve, if plugging were to occur. That is, thesecond of the two control valves would be used as a backup to the firstof the two control valves so as to keep the experiment running, ifneeded.

Prior to startup, the reactor would be pressure tested with nitrogen andpurged to ensure that no residual air or moisture would be present inthe reactor.

For startup, the organic reaction medium (anhydrous cyclohexane) wouldbe pumped using pump 180 from the organic reaction medium source 160 tothe reaction zone 110 via line 162, pump 180, line 191, mixing device190, and line 192. Once flow of the organic reaction medium wasestablished, the pressure of the reaction zone 110 would be adjusted to900 psig (6.21 MPag), and the temperature would be increased to 70° C.After the pressure and temperature were reached, hydrogen flow at 24sccm would be initiated via line 144, line 142, line 191, mixing device190, and line 192, and catalyst system flow rate in line 152 would thenbe set to 15.7 mL/h to get a reaction zone chromium concentration ofabout 0.5 ppm by mass. Catalyst system flow rate would then be set to15.7 mL/h. Thirty minutes after setting the catalyst system flow rate,ethylene would be fed at 50 g/h to the reaction zone 110 via line 142,line 191, mixing device 190, and line 192. Every 15 minutes thereafter,the ethylene flow rate would be increased by 50 g/h until 200 g/h wasreached (i.e., ethylene would be ramped to 200 g/h in 1 hour).

The first of the two control valves would plug within approximately 150minutes after beginning ethylene feed to the reaction zone 110. The runwould be terminated approximately 250 minutes after beginning ethylenefeed to the reaction zone 110 due to plugging/fouling of the autoclavereactor and additional plugging of the second of the two control valves.During the run reaction zone effluent sample would be periodicallyremoved via a sample port located on the reaction zone effluent line118. After run completion, the reactor would be disassembled, thepolymer recovered and weighed. The total amount of polymer formed inExample 1 is believed to be about 3 wt. % of the total amount of hexeneand octene produced, which would be about 25 g of polymer.

PROPHETIC EXAMPLE 2

In Example 2, the oligomerization of ethylene would be performed using1-hexene as the C₃₊ olefin during reaction zone startup.

In Example 2, a 300 cc autoclave reactor having the configuration shownin FIG. 2 would be used. The catalyst system feed line 152 would be feddirectly to the reaction zone 110, and ethylene and hydrogen from line142 would be combined with the organic reaction medium feed line 162 toyield the feedstock mixture in line 191. In Example 2, 1-hexene wouldflow through line 146, line 147 a, line 142, line 191, mixing device 190(which would be a static mixer), and line 192 to the reaction zone 110.For Example 2, the control valve 130 shown in FIG. 2 would be a pair ofcontrol valves placed in parallel flow, with the second valve of the twocontrol valves being used only upon plugging of the first control valve,if plugging were to occur. That is, the second of the two control valveswould be used as a backup to the first of the two control valves so asto keep the experiment running, if needed.

Prior to startup, the reactor would be pressure tested with nitrogen andpurged to ensure that no residual air or moisture would be present inthe reactor.

For startup, the organic reaction medium (anhydrous cyclohexane) wouldbe pumped using pump 180 from the organic reaction medium source 160 tothe reaction zone 110 via line 162, pump 180, line 191, and line 192.Once flow of the organic reaction medium was established, the pressureof the reaction zone 110 would be adjusted to 900 psig (6.21 MPag), andthe temperature would be increased to 70° C. After the pressure andtemperature were reached, hydrogen flow at 24 sccm would be initiatedvia line 144, line 142, line 191, mixing device 190, and line 192, andcatalyst system flow rate via line 152 would then be set to 15.7 mL/h toget a total concentration of Cr to about 0.5 ppm. Thirty minutes aftersetting the catalyst flow, 1-hexene flow would be initiated at 200g/hour. After 15 minutes, the 1-hexene flow rate would be reduced by 50g/hour and the ethylene flow would be initiated at 50 g/hour.Thereafter, every 15 minutes the 1-hexene flow rate would be reduced by50 g/hour and the ethylene flow rate would be increased by 50 g/houruntil the 1-hexene flow rate would become zero and the ethylene flowrate would become 200 g/hour (approximately 1 hour after initiating the1-hexene flow. The ethylene oligomerization would be continued until thecomplete consumption of the catalyst system mixture at approximately 350minutes. During the run reaction zone effluent samples would beperiodically removed via a sample port located on the reaction zoneeffluent line 118. After run completion, the reactor would bedisassembled, the polymer recovered and weighed. The total amount ofpolymer formed in Example 2 is believed to be about 2-5 g of polymer.

The total amount of polymer formed in Example 2 would be reduced byabout 10 times compared to the amount of polymer formed in Example 1.All other performance metrics including selectivity, productivity,purity, and yield would remain approximately the same between Example 1and Example 2 or the performance metrics including productivity andyield would increase for Example 2 over Example 1.

Surprisingly and unexpectedly, the presence of 1-hexene during startupin Example 2 would significantly decrease the formation of polymer whenusing the catalyst systems comprising i) a chromium component comprisinga chromium compound, ii) a heteroatomic ligand, and iii) an aluminoxane;or alternatively, i) a chromium component comprising a heteroatomicligand chromium compound complex, and ii) an aluminoxane.

While Example 2 would utilize the configuration of system 200 shown inFIG. 2, it is expected that the configuration of system 100 in FIG. 1and system 300 of FIG. 3 would perform similarly because any ethylenecan be contacted with the catalyst system in the presence of C₃₊ olefinat reaction conditions—even though no feedstock mixture is utilized inFIG. 1 and even though the contact between ethylene and the catalystsystem in FIG. 3 is outside the reaction zone 110. Thus, it is expectedthat system 100 and system 300 would have the same surprising andunexpected results as system 200.

Additional Disclosure

Accordingly, the scope of protection is not limited by the descriptionset out above but is only limited by the claims which follow, that scopeincluding all equivalents of the subject matter of the claims. Each andevery claim is incorporated into the specification as an aspect of thepresent invention. Thus, the claims are a further description and are anaddition to the detailed description of the present invention. Thedisclosures of all patents, patent applications, and publications citedherein are hereby incorporated by reference.

Embodiment 1. A process comprising: a) introducing into a reaction zonecontaining a C₃₊ olefin (any disclosed herein) and optionally an organicreaction medium (any disclosed herein) wherein the reaction zone issubstantially devoid of ethylene; i) ethylene ii) a catalyst systemcomprising (a) a chromium component comprising a chromium compound (anydescribed herein), (b) a heteroatomic ligand (any described herein), and(c) an aluminoxane (any disclosed herein); or alternatively, a catalystsystem comprising (a) a chromium component comprising a heteroatomicligand chromium compound complex (any described herein), and (b) analuminoxane (any disclosed herein), iii) the organic reaction medium,and iv) optionally hydrogen; and b) forming an ethylene oligomer productin the reaction zone; wherein the C₃₊ olefin is not an ethylene oligomerformed in-situ within the reaction zone.

Embodiment 2. A process comprising: a) contacting in a reaction zone i)a C₃₊ olefin (e.g., any disclosed herein), ii) ethylene, iii) a catalystsystem comprising (a) a chromium component comprising a chromiumcompound (any described herein), (b) a heteroatomic ligand (anydescribed herein), and (c) an aluminoxane (any disclosed herein); oralternatively, a catalyst system comprising (a) a chromium componentcomprising a heteroatomic ligand chromium compound complex (anydescribed herein), and (b) an aluminoxane (any disclosed herein), iv) anorganic reaction medium (any disclosed herein), and v) optionallyhydrogen into the reaction zone; and c) forming an ethylene oligomerproduct; wherein the C₃₊ olefin is not an ethylene oligomer formedin-situ within the reaction zone.

Embodiment 3. A process comprising: a) contacting i) ethylene, ii) acatalyst system comprising (a) a chromium component comprising achromium compound (any described herein), (b) a heteroatomic ligand (anydescribed herein), and (c) an aluminoxane (any disclosed herein); oralternatively, a catalyst system comprising (a) a chromium componentcomprising a heteroatomic ligand chromium compound complex (anydescribed herein), and (b) an aluminoxane (any disclosed herein), iii)an organic reaction medium (any described herein), and iv) optionallyhydrogen in a reaction zone; b) forming an ethylene oligomer product inthe reaction zone; wherein ethylene, the catalyst system, and theorganic reaction medium are introduced into the reaction zone and for aperiod of time a C₃₊ olefin is introduced into the reaction zone.

Embodiment 4. The process of embodiment 2 or 3, wherein ethylene, theorganic reaction medium, and for the period of time the C₃₊ olefin areseparately introduced into the reaction zone.

Embodiment 5. The process of embodiment 2 or 3, wherein ethylene and atleast a portion of the organic reaction medium are contacted to form afeedstock mixture prior to the ethylene contacting the catalyst systemand the feedstock mixture and for the period of time the C₃₊ olefin areseparately introduced to the reaction zone.

Embodiment 6. The process of embodiment 4 or 5, further comprisingintroducing the C₃₊ olefin to the reaction zone prior to introducing theethylene, the catalyst system, or both the ethylene and the catalystsystem to the reaction zone.

Embodiment 7. The process of embodiment 2 or 3, wherein ethylene, atleast a portion of the organic reaction medium, and for the period oftime the C₃₊ olefin are contacted to form a feedstock mixture prior tothe ethylene contacting the catalyst system.

Embodiment 8. A process comprising: a) feeding a catalyst system to areaction zone, the catalyst system comprising i) a chromium componentcomprising a chromium compound (any described herein), ii) aheteroatomic ligand (any described herein), and iii) an aluminoxane (anydisclosed herein); or alternatively, a catalyst system comprising i) achromium component comprising a heteroatomic ligand chromium compoundcomplex (any described herein), and ii) an aluminoxane (any disclosedherein); b) for a period of time separately feeding to the reaction zonea feedstock mixture comprising ethylene and i) a C₃₊ olefin (e.g., anydescribed herein), and ii) at least a portion of an organic reactionmedium (e.g., any described herein), or iii) combinations of i) and ii);wherein the feedstock mixture is substantially free of the catalystsystem; c) contacting the catalyst system and the feedstock mixture inthe reaction zone; and d) forming an ethylene oligomer product in thereaction zone.

Embodiment 9. A process comprising: a) contacting i) ethylene, ii) atleast a portion of an organic reaction medium (e.g., any disclosedherein), and iii) for a period of time a C₃₊ olefin (e.g., any disclosedherein) to form a feedstock mixture; b) subsequent to a), contacting ina reaction zone the feedstock mixture with a catalyst system comprisingi) a chromium component comprising a chromium compound (any describedherein), ii) a heteroatomic ligand (any described herein), and iii) analuminoxane (any disclosed herein); or alternatively, a catalyst systemcomprising i) a chromium component comprising a heteroatomic ligandchromium compound complex (any described herein), and ii) an aluminoxane(any disclosed herein); and c) forming an ethylene oligomer product inthe reaction zone.

Embodiment 10. A process comprising: a) diluting ethylene by addition ofat least i) a portion of an organic reaction medium (any describedherein), ii) for a period of time a C₃₊ olefin (e.g., any describedherein), or iii) for a period of time at least a portion of an organicreaction medium (any described herein) and a C₃₊ olefin to form afeedstock mixture prior to contacting the ethylene with a catalystsystem in a reaction zone; b) contacting in the reaction zone thefeedstock mixture and the catalyst system, wherein the catalyst systemcomprises i) a chromium component comprising a chromium compound (anydescribed herein), ii) a heteroatomic ligand (any described herein), andii) an aluminoxane (any disclosed herein); or alternatively, a catalystsystem comprising i) a chromium component comprising a heteroatomicligand chromium compound complex (any described herein), and ii) analuminoxane (any disclosed herein); and c) forming an ethylene oligomerproduct in the reaction zone.

Embodiment 11. A system comprising: a) a feedstock mixture comprisingethylene, an organic reaction medium (e.g., any described herein), andfor a period of time a C₃₊ olefin (e.g., any described herein); b) acatalyst system comprising i) a chromium component comprising a chromiumcompound (any described herein), ii) a heteroatomic ligand (anydescribed herein), and iii) an aluminoxane (any disclosed herein); oralternatively, a catalyst system comprising i) a chromium componentcomprising a heteroatomic ligand chromium compound complex (anydescribed herein), and ii) an aluminoxane (any disclosed herein); and c)a reaction zone receiving the feedstock mixture separately from thecatalyst stream.

Embodiment 12. The system of embodiment 11, further comprising areaction zone effluent line comprising an ethylene oligomer productformed in the reaction zone.

Embodiment 13. The process of any one of embodiments 7-10 or the systemof any one of embodiments 10-11, wherein for the period of time the C₃₊olefin is dispersed in the feedstock mixture prior tointroducing/feeding the feedstock mixture into the reaction zone.

Embodiment 14. The process of any one of embodiments 5-10, 13, or thesystem of any one of embodiments 11-13, wherein ethylene is dispersedwithin the feedstock mixture prior to ethylene contacting the catalystsystem.

Embodiment 15. The process of any one of embodiments 5-10, 13-14, or thesystem of any one of embodiments 11-14, wherein ethylene is dispersedwith the organic reaction medium prior to introduction of the feedstockmixture into the reaction zone.

Embodiment 16. The process of any one of embodiments 5-10, 13-15, or thesystem of any one of embodiments 10-14, wherein the period of timeoccurs during a reaction zone startup.

Embodiment 17. A process comprising: a) feeding a catalyst system to areaction zone, the catalyst system comprising i) a chromium componentcomprising a chromium compound (any described herein), ii) aheteroatomic ligand (any described herein), and iii) an aluminoxane (anydisclosed herein); or alternatively, a catalyst system comprising i) achromium component comprising a heteroatomic ligand chromium compoundcomplex (any described herein), and ii) an aluminoxane (any disclosedherein); b) separately feeding to the reaction zone a feedstock mixturecomprising i) ethylene, ii) an organic reaction medium (e.g., anydescribed herein), and iii) for a period of time a C₃₊ olefin (e.g., anydescribed herein) to contact the catalyst system; wherein during areaction zone startup the feedstock mixture C₃₊ olefin:ethylene weightratio periodically or continuously decreases; c) forming an ethyleneoligomer product in the reaction zone; and d) operating the reactionzone in about steady-state conditions subsequent to the reaction zonestart-up; wherein the feedstock mixture comprising i) ethylene, ii) aC₃₊ olefin, and iii) an organic reaction medium is fed to the reactionzone for a period of time.

Embodiment 18. A process for startup of a reaction zone, the processcomprising: for a period of time contacting in the reaction zone 1)ethylene, 2) a catalyst system comprising a) a chromium componentcomprising a chromium compound (any described herein), b) a heteroatomicligand (any described herein), and c) an aluminoxane (any disclosedherein); or alternatively, a catalyst system comprising a) a chromiumcomponent comprising a heteroatomic ligand chromium compound complex(any described herein), and b) an aluminoxane (any disclosed herein), 3)an organic reaction medium, and 4) optionally hydrogen to form anethylene oligomer product; wherein: the catalyst system is fed to thereaction zone, a feedstock mixture comprising i) ethylene, ii) anorganic reaction medium (any described herein), and iii) a C₃₊ olefin(any described herein) is fed to the reaction zone for a period of time,wherein the feedstock mixture is substantially free of the catalystsystem prior to the feedstock mixture contacting the catalyst system inthe reaction zone.

Embodiment 19. The process of embodiment 17 or 18, wherein for theperiod of time the C₃₊ olefin is dispersed in the feedstock mixtureprior to introducing/feeding the feedstock mixture into the reactionzone.

Embodiment 20. The process of any one of embodiments 17-19, whereinethylene is dispersed within the feedstock mixture prior to ethylenecontacting the catalyst system.

Embodiment 21. The subject matter of any one of embodiments 5-20,wherein the period of time begins at a point when the reaction zone isnot producing the ethylene oligomer product.

Embodiment 22. The subject matter of any one of embodiments 5-21,wherein over a C₃₊ olefin/ethylene feed period of time period of time aC₃₊ olefin:ethylene weight ratio fed/introduced to the reaction zonedecreases from a value of at least 0.5:1 (or any other at least valuedisclosed herein) to a value less than 0.2:1 (or any other less thanvalue disclosed herein).

Embodiment 23. The subject matter of any one of embodiments 5-22,wherein the C₃₊ olefin:ethylene weight ratio has an initial value ofabout 1:0.

Embodiment 24. The subject matter of any one of embodiments 5-23,wherein the C₃₊ olefin:ethylene weight ratio decreases to a value ofabout 0:1.

Embodiment 25. The subject matter of any one of embodiments 1-24,wherein over a reaction zone period of time the reaction zone has a C₃₊olefin to ethylene zone weight ratio that decreases from a value of atleast 0.5:1 (or any other reaction zone at least value disclosed herein)to a value less than 0.2:1 (or any other reaction zone less than valuedisclosed herein), wherein the C₃₊ olefin in the reaction zone and theC₃₊ olefin of the C₃₊ olefin:ethylene weight ratio is not an ethyleneoligomer formed in-situ within the reaction zone.

Embodiment 26. The subject matter of any one of embodiments 1-25,further comprising contacting the C₃₊ olefin with the catalyst systemprior to introducing (or feeding) the C₃₊ olefin and the catalyst systemto the reaction zone.

Embodiment 27. The subject matter of any one of embodiments 1-26,wherein substantially no C₃₊ olefin is introduced or fed to the reactionzone after the period of time, wherein the period of time is a reactionzone period of time or a C₃₊ olefin/ethylene feed period of time.

Embodiment 28. The subject matter of any one of embodiments 1-27,wherein the reaction zone is operated under steady-state conditionsafter the period of time (or subsequent to the reaction zone start-upperiod), wherein the period of time is a reaction zone period of time ora C₃₊ olefin/ethylene feed period of time.

Embodiment 29. The subject matter of any one of embodiments 1-27,wherein the contacting of ethylene and the organic reaction medium toform the feedstock mixture occurs subsequently, but not exclusively,after the period of time (or after reaction zone startup), wherein theperiod of time is a reaction zone period of time or a C₃₊olefin/ethylene feed period of time.

Embodiment 30. The subject matter of any one of embodiments 27-29,wherein substantially all of the ethylene is introduced to the reactionzone via the feedstock mixture.

Embodiment 31. The subject matter of any one of embodiment 27-30,wherein the catalyst system is introduced into the reaction zoneseparately from feedstock mixture.

Embodiment 32. The subject matter of any one of embodiments 1-31,wherein the at least a portion of the organic reaction medium iscontacted with an alkylaluminum compound prior to introduction of the atleast a portion of the organic reaction medium to the reaction zone.

Embodiment 33. The subject matter of any one of embodiments 1-32,wherein the at least a portion of the organic reaction medium iscontacted with an alkylaluminum compound prior to contact of ethylenewith the at least a portion of the organic reaction medium.

Embodiment 34. The subject matter of any one of embodiments 1-33,wherein the catalyst system mixture comprises a diluent.

Embodiment 35. The subject matter of embodiment 36, wherein the diluentcomprises the organic reaction medium.

Embodiment 36. The subject matter of any one of embodiments 1-34,wherein a reaction zone effluent comprising the ethylene oligomerproduct is removed from the reaction zone.

Embodiment 37. The subject matter of any one of embodiments 1-36,wherein hexenes and/or or octenes are separated from the reaction zoneeffluent.

Embodiment 38. The subject matter of any one of embodiments 1-37,wherein the feedstock mixture, the catalyst system, and optionally,hydrogen are periodically or continuously introduced into the reactionzone and a reaction zone effluent comprising the ethylene oligomerproduct is periodically or continuously removed from the reaction zone.

Embodiment 39. The subject matter of any one of embodiments 1-38,wherein a mass of polymer per mass of oligomer in the reaction zone isless than the mass of polymer per mass of oligomer in the reaction zonein an otherwise similar process or system where a C₃₊ olefin:ethyleneweight ratio does not decrease over the period of time.

Embodiment 40. The subject matter of any one of embodiments 1-39,wherein a mass of polymer per mass of oligomer in the reaction zone isless than the mass of polymer per mass of oligomer in the reaction zonein an otherwise similar process or system which does not: i) contactethylene with the at least a portion of the organic reaction mediumprior to contact of ethylene with the catalyst system, or ii) introduceor feed the feedstock mixture into the reaction zone separately from thecatalyst system.

Embodiment 41. The subject matter of any one of embodiments 1-40, havinga productivity higher than a productivity in an otherwise similarprocess or system where the reaction zone C₃₊ olefin:ethylene weightratio does not decrease over the period of time.

Embodiment 42. The subject matter of any one of embodiments 1-41, havinga productivity higher than a productivity in an otherwise similarprocess or system which does not: i) contact ethylene with the at leasta portion of the organic reaction medium prior to contact of ethylenewith the catalyst system, or ii) introduce or feed the feedstock mixtureinto the reaction zone separately from the catalyst system.

Embodiment 43. A reaction system comprising: a reaction zone; a firstreaction zone inlet configured to introduce a catalyst system comprising(a) a chromium component comprising a chromium compound (any describedherein), (b) a heteroatomic ligand (any described herein), and (c) analuminoxane (any disclosed herein); or alternatively, a catalyst systemcomprising (a) a chromium component comprising a heteroatomic ligandchromium compound complex (any described herein), and (b) an aluminoxane(any disclosed herein) to the reaction zone; a second reaction zoneinlet configured to introduce ethylene, an organic reaction medium, andoptionally hydrogen to the reaction zone; a C₃₊ olefin feed line influid communication with the first reaction zone inlet, the secondreaction zone inlet, or a third reaction zone inlet configured tointroduce a C₃₊ olefin to the reaction zone; and one or more reactionzone outlets configured to discharge the reaction zone effluentcomprising an ethylene oligomer product from the reaction zone.

Embodiment 44. The reaction system of embodiment 43, further comprising:a catalyst system feed line flowing the catalyst system to the firstreaction zone inlet; an ethylene feed line comprising the ethylene; anorganic reaction medium feed line comprising the organic reactionmedium, wherein the organic reaction medium feed line and the ethylenefeed line combine to yield the feedstock mixture which is introduced tothe reaction zone via the second reaction zone inlet, wherein the C₃₊olefin feed line combines with at least one of the catalyst system feedline, the ethylene feed line, the organic reaction medium feed line, thefeedstock mixture feed line, or a dispersed feedstock mixture feed lineformed by passing the feedstock mixture through a mixing device prior toflowing to the reaction zone via the second reaction zone inlet.

Embodiment 45. The reaction system of embodiment 43 or 44, furthercomprising: a pump in fluid communication with the second reaction zoneinlet and which is located upstream of a point where the ethylene feedline and the organic reaction medium feed line join to produce thefeedstock mixture; and a mixing device positioned between i) the joiningof the ethylene feed line and the organic reaction medium feed line andii) the second reaction zone inlet to disperse the ethylene and theorganic reaction medium prior to the feedstock mixture entering thereaction zone.

Embodiment 46. The reaction system of any one of embodiments 43-45,wherein during steady state operation, the first reaction zone inlet isconfigured to periodically or continuously introduce the catalyst systemto the reaction zone, the second reaction zone inlet is configured toperiodically or continuously introduced the feedstock mixture to thereaction zone, and the one or more reaction zone outlets are configuredto periodically or continuously discharge the reaction zone effluentfrom the reaction zone.

Embodiment 47. A reaction system comprising: a reaction zone; a reactionzone inlet configured to introduce a catalyst system, ethylene, anorganic reaction medium, and a C₃₊ olefin to the reaction zone; anethylene feed line comprising ethylene, a C₃₊ olefin feed linecomprising a C₃₊ olefin, an organic reaction medium feed line comprisingan organic reaction medium and optionally a hydrogen feed linecomprising hydrogen all in fluid communication with the reaction zoneinlet, wherein the organic reaction medium feed line combines with theethylene feed line to form a feedstock mixture feed line in fluidcommunication with the reaction zone inlet; a catalyst system feed linecomprising catalyst system in fluid communication with the reaction zoneinlet, wherein the catalyst system feed line combines with the ethylenefeed line, the organic reaction medium feed line, the feedstock mixturefeed line, or a dispersed feedstock mixture feed line formed by passingthe feedstock mixture feed line through a mixing device; one or morereaction zone outlets configured to discharge the reaction zone effluentcomprising an ethylene oligomer product from the reaction zone, whereinthe catalyst system comprises (a) a chromium component comprising achromium compound (any described herein), (b) a heteroatomic ligand (anydescribed herein), and (c) an aluminoxane (any disclosed herein); oralternatively, a catalyst system comprising (a) a chromium componentcomprising a heteroatomic ligand chromium compound complex (anydescribed herein), and (b) an aluminoxane (any disclosed herein), andwherein the C₃₊ olefin feed line joins with one or more of the ethylenefeed line, the organic reaction medium feed line, the feedstock mixturefeed line, the dispersed feedstock mixture feed line, or a combined feedline formed by joining the catalyst system feed line and the dispersedfeedstock mixture feed line.

Embodiment 48. The reaction system of embodiment 47, further comprising:a mixing device positioned between i) the joining of the ethylene feedline and the organic reaction medium feed line and ii) the reaction zoneinlet to disperse the ethylene and the organic reaction medium prior tothe feedstock mixture joining with the catalyst system and entering thereaction zone.

Embodiment 49. The reaction system of any one of embodiments 47-48,wherein the reaction zone inlet is configured to periodically orcontinuously introduce the catalyst system and the feedstock mixture tothe reaction zone, and the one or more reaction zone outlets areconfigured to periodically or continuously discharge the reaction zoneeffluent from the reaction zone.

Embodiment 50. A reaction system comprising: a reaction zone; a firstreaction zone inlet configured to introduce a catalyst system comprising(a) a chromium component comprising a chromium compound (any describedherein), (b) a heteroatomic ligand (any described herein), and (c) analuminoxane (any disclosed herein); or alternatively, a catalyst systemcomprising (a) a chromium component comprising a heteroatomic ligandchromium compound complex (any described herein), and (b) an aluminoxane(any disclosed herein) to the reaction zone; a second reaction zoneinlet configured to introduce ethylene and optionally hydrogen to thereaction zone; a third reaction zone inlet configured to introduce anorganic reaction medium to the reaction zone; a C₃₊ olefin feed line influid communication with one or more of the first reaction zone inlet,the second reaction zone inlet, the third reaction zone inlet, or afourth reaction zone inlet which is configured to introduce the C₃₊olefin directly to the reaction zone; and one or more reaction zoneoutlets configured to discharge the reaction zone effluent comprising anethylene oligomer product from the reaction zone.

Embodiment 51. The reaction system of embodiment 50, further comprising:a catalyst system feed line flowing the catalyst system to the firstreaction zone inlet; an ethylene feed line comprising flowing ethyleneto the second reaction zone inlet; and an organic reaction medium feedline flowing the organic reaction medium to the third reaction zoneinlet, wherein the C₃₊ olefin feed line i) combines with at least one ofthe catalyst system feed line, the ethylene feed line, or the organicreaction medium feed line, or ii) flows directly to the fourth reactionzone inlet.

Embodiment 52. The subject matter of any one of embodiments 1-51,wherein the C₃₊ olefin comprises a C₄ to C₁₆ internal olefin or alphaolefin.

Embodiment 53. The subject matter of any one of embodiments 1-51,wherein the C₃₊ olefin comprises 1-hexene, 1-octene, or 1-hexene and1-octene.

Embodiment 54. The subject matter of any one of embodiments 1-53,wherein the heteroatomic ligand has the structure

(or alternatively, the heteroatomic ligand chromium complex has thestructure

where each X^(1s) is independently selected from the group consisting ofN, P, O, and S; L^(1s) is an organylene linking group linking X^(1s)s; mand n are independently 1 or 2; each R^(1s) is independently an organylgroup; X is a monoanionic ligand; and p is from 2 to 6.

The inventions illustratively disclosed herein suitably can be practicedin the absence of any element that is not specifically disclosed hereinand/or any optional element disclosed herein. While compositions andmethods are described in terms of “comprising,” “containing,” or“including” various components or steps, the compositions and methodscan also “consist essentially of” or “consist of” the various componentsand steps. All numbers and ranges disclosed above can vary by someamount. Whenever a numerical range with a lower limit and an upper limitis disclosed, any number and any included range falling within the rangeare specifically disclosed. In particular, every range of values (of theform, “from about a to about b,” or, equivalently, “from approximately ato b,” or, equivalently, “from approximately a-b”) disclosed herein isto be understood to set forth every number and range encompassed withinthe broader range of values.

All publications and patents mentioned herein are incorporated herein byreference. The publications and patents mentioned herein can be utilizedfor the purpose of describing and disclosing, for example, theconstructs and methodologies that are described in the publications,which might be used in connection with the presently describedinvention. The publications discussed throughout the text are providedsolely for their disclosure prior to the filing date of the presentapplication. Nothing herein is to be construed as an admission that theinventors are not entitled to antedate such disclosure by virtue ofprior invention.

Therefore, the present invention is well adapted to attain the ends andadvantages mentioned as well as those that are inherent therein. Thisconcludes the detailed description. The particular embodiments disclosedabove are illustrative only, as the invention can be modified andpracticed in different but equivalent manners apparent to those skilledin the art having the benefit of the teachings herein. Furthermore, nolimitations are intended to the details of construction or design hereinshown, other than as described in the claims below. It is thereforeevident that the particular embodiments disclosed above can be alteredor modified and all such variations are considered within the scope andspirit of the invention. Accordingly, the protection sought herein is asset forth in the claims herein.

What is claimed is:
 1. A reaction system comprising: a reaction zonecomprising ethylene, an organic reaction medium, a catalyst system, aC₃₊ olefin, and optionally hydrogen and having a C₃₊ olefin:ethyleneweight ratio that decreases from a value of equal to or greater than0.5:1 to a value less than 0.2:1 over a period of time; a first reactionzone inlet connected to the reaction zone and configured to introducethe catalyst system comprising i) a chromium component comprising aheteroatomic ligand chromium compound complex, and ii) an aluminoxane tothe reaction zone; a second reaction zone inlet connected to thereaction zone and configured to introduce a feedstock mixture comprisingethylene, at least a portion of the organic reaction medium, andoptionally hydrogen to the reaction zone; a C₃₊ olefin feed line influid communication with the first reaction zone inlet, the secondreaction zone inlet, or a third reaction zone inlet, wherein the C₃₊olefin feed line is configured to introduce the C₃₊ olefin to thereaction zone; and one or more reaction zone outlets connected to thereaction zone and configured to discharge a reaction zone effluentcomprising an ethylene oligomer product from the reaction zone; whereinthe C₃₊ olefin in the reaction zone that is used to determine the C₃₊olefin:ethylene weight ratio in the reaction zone is not an ethyleneoligomer formed in-situ within the reaction zone, wherein theheteroatomic ligand chromium compound complex has the formula

where each X^(1s) is independently selected from the group consisting ofN, P, O, and S; L^(1s) is a C₁ to C₂₀ organylene linking group, a C₁ toC₃₀ amin-di-yl group, or a C₁ to C₃₀ phosphin-di-yl group linking X^(1s)s; each m is independently 1 or 2; each R^(1s) is independently a C₁ toC₂₀ organyl group; X is a halide, a C₁ to C₂₀ carboxylate, a C₁ to C₂₀β-diketonate, or a C₁ to C₂₀ hydrocarboxide; and p is from 2 to
 6. 2.The reaction system of claim 1, further comprising: a catalyst systemfeed line connected to the first reaction zone inlet and configured toflow the catalyst system to the first reaction zone inlet.
 3. Thereaction system of claim 2, wherein the C₃₊ olefin feed line isconnected to the catalyst system feed line.
 4. The reaction system ofclaim 1, further comprising: an ethylene feed line comprising ethyleneand optionally hydrogen; and an organic reaction medium feed linecomprising the organic reaction medium, wherein the ethylene feed lineand the organic reaction medium feed line are configured to combine toform a feedstock mixture line comprising the feedstock mixture, whereinthe feedstock mixture line is connected to or coupled to the secondreaction zone inlet.
 5. The reaction system of claim 4, wherein the C₃₊olefin feed line is connected to the organic reaction medium feed line.6. The reaction system of claim 4, wherein the C₃₊ olefin feed line isconnected to the ethylene feed line.
 7. The reaction system of claim 4,wherein the C₃₊ olefin feed line is connected to the feedstock mixtureline.
 8. The reaction system of claim 4, further comprising: a mixingdevice positioned between i) the joining of the ethylene feed line andthe organic reaction medium feed line and ii) the second reaction zoneinlet, to disperse the ethylene and the organic reaction medium in thefeedstock mixture prior to the feedstock mixture entering the reactionzone; and a pump located in the organic reaction medium feed line. 9.The reaction system of claim 8, wherein the C₃₊ olefin feed line isconnected to a dispersed line formed by passing the feedstock mixturethrough the mixing device prior to flowing to the reaction zone via thesecond reaction zone inlet.
 10. The reaction system of claim 1, whereinthe organic reaction medium is an aliphatic hydrocarbon.
 11. Thereaction system of claim 1, wherein the C₃₊ olefin comprises hexene,1-octene, or a combination thereof; and wherein the ethylene oligomerproduct comprises hexenes and/or octenes.
 12. The reaction system ofclaim 1, wherein the catalyst system is fed into the reaction zoneseparately of the feedstock mixture.
 13. A reaction system comprising: areaction zone comprising ethylene, an organic reaction medium, acatalyst system, a C₃₊ olefin, and optionally hydrogen and having a C₃₊olefin:ethylene weight ratio that decreases from a value of equal to orgreater than 0.5:1 to a value less than 0.2:1 over a period of time; afirst reaction zone inlet connected to the reaction zone and configuredto introduce the catalyst system comprising i) a chromium componentcomprising a heteroatomic ligand chromium compound complex, and ii) analuminoxane to the reaction zone; a second reaction zone inlet connectedto the reaction zone and configured to introduce ethylene and optionallyhydrogen to the reaction zone; a third reaction zone inlet connected tothe reaction zone and configured to introduce at least a portion of theorganic reaction medium to the reaction zone; a C₃₊ olefin feed line influid communication with the first reaction zone inlet, the secondreaction zone inlet, the third reaction zone inlet, or a fourth reactionzone inlet, wherein the C₃₊ olefin feed line is configured to introducethe C₃₊ olefin to the reaction zone; and one or more reaction zoneoutlets connected to the reaction zone and configured to discharge areaction zone effluent comprising an ethylene oligomer product from thereaction zone, wherein the C₃₊ olefin in the reaction zone that is usedto determine the C₃₊ olefin:ethylene weight ratio in the reaction zoneis not an ethylene oligomer formed in-situ within the reaction zone,wherein the heteroatomic ligand chromium compound complex has theformula

where each X^(1s) is independently selected from the group consisting ofN, P, O, and S; L^(1s) is a C₁ to C₂₀ organylene linking group, a C₁ toC₃₀ amin-di-yl group, or a C₁ to C₃₀ phosphin-di-yl group linkingX^(1s)s; each m is independently 1 or 2; each R^(1s) is independently aC₁ to C₂₀ organyl group; X is a halide, a C₁ to C₂₀ carboxylate, a C₁ toC₂₀ β-diketonate, or a C₁ to C₂₀ hydrocarboxide; and p is from 2 to 6.14. The reaction system of claim 13, further comprising: a catalystsystem feed line connected to the first reaction zone inlet andconfigured to flow the catalyst system to the first reaction zone inlet;an ethylene feed line connected to the second reaction zone inlet andcomprising the ethylene and optionally hydrogen, wherein the ethylenefeed line is configured to flow ethylene and optionally hydrogen to thereaction zone via the second reaction zone inlet; and an organicreaction medium feed line connected to the third reaction zone inlet andcomprising the organic reaction medium and configured to flow the atleast a portion of the organic reaction medium to the reaction zone viathe third reaction zone inlet, where the C₃₊ olefin feed line isconnected to the catalyst system feed line, the ethylene feed line, theorganic reaction medium feed line, or the fourth reaction zone inlet.15. The reaction system of claim 13, wherein the catalyst system is fedinto the reaction zone separately from ethylene.
 16. A reaction systemcomprising: a reaction zone comprising ethylene, an organic reactionmedium, a catalyst system, a C₃₊ olefin, and optionally hydrogen andhaving a C₃₊ olefin:ethylene weight ratio that decreases from a value ofequal to or greater than 0.5:1 to a value less than 0.2:1 over a periodof time; a first reaction zone inlet connected to the reaction zone andconfigured to introduce ethylene, at least a portion of the organicreaction medium, optionally hydrogen, and the catalyst system comprisingi) a chromium component comprising a heteroatomic ligand chromiumcompound complex, and ii) an aluminoxane to the reaction zone; a C₃₊olefin feed line in fluid communication with the first reaction zoneinlet or a second reaction zone inlet, wherein the C₃₊ olefin feed lineis configured to introduce the C₃₊ olefin to the reaction zone; and oneor more reaction zone outlets connected to the reaction zone andconfigured to discharge a reaction zone effluent comprising an ethyleneoligomer product from the reaction zone, wherein the C₃₊ olefin in thereaction zone that is used to determine the C₃₊ olefin:ethylene weightratio in the reaction zone is not an ethylene oligomer formed in-situwithin the reaction zone, wherein the heteroatomic ligand chromiumcompound complex has the formula

where each X^(1s) is independently selected from the group consisting ofN, P, O, and S; L^(1s) is a C₁ to C₂₀ organylene linking group, a C₁ toC₃₀ amin-di-yl group, or a C₁ to C₃₀ phosphin-di-yl group linking X^(1s)s; each m is independently 1 or 2; each R^(1s) is independently a C₁ toC₂₀ organyl group; X is a halide, a C₁ to C₂₀ carboxylate, a C₁ to C₂₀β-diketonate, or a C₁ to C₂₀ hydrocarboxide; and p is from 2 to
 6. 17.The reaction system of claim 16, further comprising: an ethylene feedline comprising ethylene and optionally hydrogen, wherein the ethylenefeed line is configured to flow ethylene and optionally hydrogen to thereaction zone via the first reaction zone inlet; an organic reactionmedium feed line comprising the organic reaction medium, wherein theorganic reaction medium feed line is configured to flow the at least aportion of the organic reaction medium to the reaction zone via thefirst reaction zone inlet; and a catalyst system feed line configured toflow the catalyst system to reaction zone via the first reaction zoneinlet.
 18. The reaction system of claim 17, wherein the C₃₊ olefin feedline is connected to the ethylene feed line, the organic reaction mediumfeed line, or the catalyst system feed line.
 19. The reaction system ofclaim 17, wherein the organic reaction medium feed line and the ethylenefeed line are configured to combine to form a feedstock mixture linethat is connected to or coupled to the first reaction zone inlet. 20.The reaction system of claim 19, wherein the C₃₊ olefin feed line isconnected to the feedstock mixture line.
 21. The reaction system ofclaim 19, further comprising: a mixing device positioned between i) thejoining of the ethylene feed line and the organic reaction medium feedline and ii) the first reaction zone inlet, to disperse the ethylene andthe organic reaction medium in a feedstock mixture prior to thefeedstock mixture entering the reaction zone.
 22. The reaction system ofclaim 21, wherein the C₃₊ olefin feed line is connected to a dispersedline formed by passing the feedstock mixture through the mixing deviceprior to flowing to the reaction zone via the first reaction zone inlet.23. The reaction system of claim 21, wherein the catalyst system feedline is configured to combine with a dispersed line formed by passingthe feedstock mixture through the mixing device prior to flowing to thereaction zone, to form a combined feed line, wherein the combined feedline is connected to the first reaction zone inlet.
 24. The reactionsystem of claim 23, wherein the C₃₊ olefin feed line is connected to thedispersed line or the combined feed line.